JP3705801B1 - Lithium ion secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithium ion secondary battery having excellent safety and battery performance, particularly in a large-sized lithium ion secondary battery having a battery capacity of 5 Ah or more and an electric capacity per cm ² of a positive electrode and a negative electrode of 10 mAh or more. The purpose is to propose the next battery.
SOLUTION: The lithium ion secondary battery of the present invention has not only a high potential / high energy density and high safety / stability, but also has iron as a main component as a positive electrode active material. The olivine type LiFePO ₄ which is a material realizing a low environmental load is used. In addition, γ-butyrolactone has the properties of having both high dielectric constant and low viscosity, excellent oxidation resistance, high boiling point, low vapor pressure, high flash point, etc. Used for water electrolyte. By these things, compared with the lithium ion secondary battery as a conventional power supply for portable devices, the large sized lithium ion secondary battery excellent in safety can be provided.
[Selection] Figure 1

Description

  The present invention relates to a chargeable / dischargeable secondary battery, and more particularly to a large lithium ion secondary battery.

  A lithium ion secondary battery using a metal oxide for the positive electrode, an organic electrolyte for the electrolyte, and a carbon material such as graphite for the negative electrode was first commercialized in 1991. Since then, its high energy density makes it compact and lightweight. It has rapidly become popular for portable electronic devices such as video cameras, mobile phones, notebook computers, and minidiscs.

  Many of the lithium ion secondary batteries that are power sources of these portable electronic devices have a thickness of 200 to 300 μm obtained by applying or pressing a composite material containing an electrode active material to a current collector made of a perforated metal plate or metal foil. A film-like electrode is wound or laminated together with a separator, and the wound or laminated film-like electrode is sealed in a cylindrical or rectangular outer can. Since the electrodes of these batteries are thin, the electrode area can be increased, and high rate charge / discharge is possible.

  As electrolytes for lithium ion secondary batteries, chain carbonates such as diethyl carbonate, ethyl methyl carbonate and dimethyl carbonate, cyclic carbonates such as propylene carbonate and ethylene carbonate, or cyclic esters such as γ-butyrolactone and γ-valerolactone Alternatively, a nonaqueous electrolytic solution in which a Li salt is dissolved in an organic solvent in which two or more of these are mixed is used. In particular, in order to smoothly move lithium ions in a low temperature environment, it is common to use a chain carbonate mixed with a cyclic carbonate.

  Among such lithium ion secondary batteries, a square battery can be used more efficiently when mounted on a device than a cylindrical battery, and can also be easily used as a battery as a battery pack. In the case of this rectangular battery, the stacked structure of strip electrodes is more advantageous than the wound structure in order to increase the filling rate of the electrode group with respect to the volume inside the battery.

  In the case of a stacked type square battery, when the electric capacity is increased, a technique for stacking a plurality of positive electrodes and negative electrodes accurately aligned is required. On the other hand, when the thickness of the electrode is increased, there is no need to align the positions of such a large number of positive electrodes and negative electrodes, but the electrode active material falls off during charging / discharging, and the capacity of the battery decreases. Problem arises. Therefore, for such problems, for example, as a conventional technique, a technique of using a porous sheet made of aluminum fibers as a core material of a positive electrode (see Patent Document 1), or holding a negative electrode active material in a metal porous body An electrode technology (see Patent Document 2) has been proposed.

In addition, lithium cobalt oxide (LiCoO ₂ ) containing cobalt (Co) that has been used in the positive electrode so far has less reserve than iron (Fe) and Mn (manganese), and is used continuously. Has a problem. In recent years, olivine-type LiFePO ₄ containing iron as a main component has attracted attention as a low environmental load and ultra-low cost positive electrode material. For example, as a conventional technique, a technique for improving the electron conductivity of the positive electrode by mixing an active material of olivine type LiFePO ₄ with a noble conductive material having a higher redox potential (see Patent Document 3), an olivine type A technique has been proposed in which a part of LiFePO ₄ is replaced with fluorine to reduce the electrical resistance of the positive electrode active material and increase the conductivity (see Patent Document 4).

  Further, as described above, an organic electrolyte is used as an electrolyte in the lithium ion secondary battery. For this reason, with regard to safety, several measures are taken, and it is designed not to cause an accident such as rupture or ignition even under severe use conditions. For example, it is designed to prevent accidents due to overcharge and overdischarge by attaching a protection circuit, and as a safety measure when the temperature of the battery rises, the conductive path from the terminal to the inside of the battery is In part, a PTC (Positive Temperature Coefficient) element is used in which the electrical resistance increases to almost infinite when the temperature exceeds a certain value.

  Even if such safety measures are implemented, current flows in a short-circuited location due to external factors (for example, when a nail is pierced) or an internal short circuit, and heat is generated by resistance heat generation. There is a possibility of so-called “thermal runaway” that causes a chemical reaction of the active material and electrolyte in the tubule, which may eventually lead to rupture and ignition. As one of the countermeasures, in a small lithium ion secondary battery, when the battery temperature rises, the separator melts, the hole of the separator is blocked and an insulating film is prevented from flowing current. Functions such as “shutdown function” are provided. In addition, a safety valve or the like is provided so that the battery does not burst when the internal pressure of the lithium ion secondary battery rises abnormally.

In addition, lithium ion secondary batteries have higher energy efficiency (power efficiency) in charge and discharge compared to lead-acid batteries and nickel metal hydride, so they are promising for electric vehicles and power storage applications. Has been promoted. In addition, medium-sized lithium ion secondary batteries are partly put into practical use in applications such as bicycles with electric assistance. The development of these medium-sized to large-sized batteries has been promoted by following the battery structure obtained in the development of small batteries.
JP-A-6-196170 JP-A-7-22021 JP 2001-110414 A JP 2003-187799 A

While producing the lithium ion secondary battery by this prior art, the charging / discharging test of the produced lithium ion secondary battery was done. First, the produced lithium ion secondary battery will be described below. Lithium cobalt oxide (LiCoO ₂ ) was used as the positive electrode active material, 20 parts by weight of ketjen black as a conductive material, 10 parts by weight of polyvinylidene fluoride (hereinafter referred to as PVdF) as a binder (binder), and N-methyl as a solvent. A positive electrode paste was prepared using -2-pyrrolidone (hereinafter referred to as NMP). The paste thus obtained was filled in foamed aluminum (size: 10 cm × 20 cm, thickness 4 mm, porosity 92%), dried sufficiently, and then pressed using a hydraulic press to obtain a thickness of 3. A 0 mm electrode was obtained. The weight of the active material per area of the obtained electrode was 210 mg / cm ² , and the porosity of the positive electrode was 55%. In the present specification, “parts by weight” is a value expressed as a percentage of the weight ratio of the positive electrode active material to the weight.

For the negative electrode active material, artificial graphite powder (average particle size 12 μm, d002 = 0.3365 nm, BET specific surface area 7 m ² / g) was used, 12 parts by weight of PVdF was added as a binder, and NMP was used as a solvent to form a negative electrode paste. Produced. The paste thus obtained was filled into a non-woven fabric of copper fibers (size: 10.2 cm × 20.2 cm, thickness 2.5 mm, porosity 88%), sufficiently dried, and then using a hydraulic press. It pressed and obtained the electrode of thickness 1.5mm. The amount of active material per area of the obtained electrode was 95 mg / cm ² , and the porosity of the negative electrode was 50%. In this specification, “d002” is graphite having a layered crystal structure and is defined as an interval between adjacent layers (interval between (002) planes). Further, the “BET specific surface area” is an area per weight of pores capable of adsorbing nitrogen at 77 K, which is obtained by using the BET formula obtained by extending the monomolecular layer adsorption theory to a multimolecular layer.

  Also, as a separator that is a member that separates both electrodes to prevent a short circuit due to direct contact between the positive electrode and the negative electrode, two microporous membranes made of polyethylene with a thickness of 25 μm were used, and the obtained electrode was One positive electrode and one negative electrode were laminated so as to face each other and inserted into a bag-shaped aluminum laminate.

Then, as a non-aqueous electrolyte, borofluoride is added to a solvent in which γ-butyrolactone (hereinafter referred to as GBL) and ethylene carbonate (hereinafter referred to as EC) are mixed at a volume ratio of 7: 3 so that the concentration is 1.5 mol / l. A solution in which lithium bromide (LiBF ₄ ) is dissolved is used. This non-aqueous electrolyte is poured into an aluminum laminate bag into which a laminate of electrodes is inserted, and then sealed by thermal fusion, thereby producing a lithium ion secondary battery having a design capacity of 5 Ah. .

  The battery obtained as described above was subjected to a charge / discharge test under the following conditions. When charging, charging is performed until the charging current is 1.5 A and the voltage is 4.2 V, and then 15 hours elapses at the voltage 4.2 V, or the charging is terminated when the charging current is 0.1 A. When discharging, the discharge is performed until the discharge current is 1.5A and the voltage is 2.75V. After charging and discharging 100 times under such conditions, the battery is further charged to the full capacity. The battery capacity of the lithium ion secondary battery thus fully charged was measured, and further, a nail penetration test for penetrating a 2.5 mmφ nail was performed with the battery laid sideways. As shown in FIG. 5, not only the battery capacity after charging and discharging is repeated 100 times, but also the result of the nail penetration test is that white smoke is generated and a dangerous state is caused. There is a problem.

  In this way, in the large lithium ion secondary battery manufactured simply by increasing the size following the structure of the conventional small battery, only the safety measures applied to the small lithium ion secondary battery described above are used. Is not enough.

In addition, when a chain carbonate such as diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate or the like is used in the electrolyte, the vapor pressure of the solvent increases, and a large amount of gas is generated in a high temperature environment. For this reason, in a lithium ion secondary battery containing a lot of chain carbonates, problems such as expansion and deformation of the outer package arise. Furthermore, when chain carbonate is included in the electrolytic solution, the amount of heat generated when a battery overcharge test or thermal test is performed during production is large. For this reason, in order to ensure sufficient safety, in addition to providing a protection circuit for preventing overcharge, it is necessary to use a plurality of protection mechanisms such as a safety valve, a current cutoff valve, a PTC element, etc. There is a problem that the battery becomes complicated and the energy density of the battery decreases. This problem is particularly noticeable in large-sized lithium ion secondary batteries.

In view of such a problem, the present invention is a large-sized lithium ion secondary battery having a battery capacity of 5 Ah or more and an electric capacity per cm ² of the positive electrode and the negative electrode of 10 mAh or more. The object is to propose a good lithium ion secondary battery.

In order to achieve the above object, a lithium ion secondary battery of the present invention includes a positive electrode including a current collector having a positive electrode active material, a negative electrode including a current collector having a negative electrode active material, the positive electrode, and the positive electrode. a separator to prevent the negative electrode are short-circuited by the physical contact, a lithium ion secondary battery and a nonaqueous electrolytic solution containing a lithium salt, the battery capacity is more than 5Ah, and the The positive electrode and the negative electrode have an electric capacity per 1 cm ² of 10 mAh or more, the positive electrode active material is olivine-type LiFePO ₄ , and the current collector is a three-dimensional porous metal body having a plurality of pores. And the non-aqueous electrolyte contains at least γ-butyrolactone ,
The content of the γ- butyrolactone contained in the nonaqueous electrolyte, characterized in der Rukoto 50% to 80% in volume fraction.

In such a lithium ion secondary battery, the nonaqueous safety small Kunar and large lithium ion secondary battery wherein the γ- butyrolactone content than 50% by volume fraction in the electrolyte solution is lowered. Further, the well γ- butyrolactone size Kunar and electrodes content of from 80%, other members constituting the lithium ion secondary battery, for example, low permeability of the non-aqueous electrolyte into the separator, etc. it decreases the performance of the lithium ion secondary battery. A gel electrolyte or the like may be used as the non-aqueous electrolyte. In addition, since the metal porous body having a three-dimensional structure including a plurality of pores is used for the current collector that constitutes the electrode, a metal having excellent thermal conductivity is formed throughout the electrode inside the lithium ion secondary electrode. By being uniformly present, it is possible to improve the heat dissipation in the electrode. This makes it possible to further increase safety.

  In the lithium ion secondary battery of the present invention, the thickness of at least one of the positive electrode and the negative electrode is 1 mm or more and less than 10 mm.

In such a lithium ion secondary battery, when the thickness of at least one of the positive electrode and the negative electrode is 10 mm or more , as a result, the non-aqueous electrolyte does not sufficiently permeate the positive electrode and the negative electrode, resulting in performance. it becomes difficult to maintain. The thickness of the electrode is less than the smaller Kunar and inside the electrode porosity 1 mm, also, the positive active material and the to the weight of the negative electrode active material is reduced, it intends want more and more laminated sheets.

  The lithium ion secondary battery according to the present invention includes a plurality of the negative electrode and the separator, and the negative electrode is disposed on both sides of the positive electrode so as to sandwich the positive electrode through the separator.

  In such a lithium ion secondary battery, by increasing the thickness of the positive electrode, the negative electrode is arranged on both sides of the positive electrode, and the polarization of the negative electrode can be reduced, so that lithium deposition can be avoided. Become. In this case, the thick positive electrode is sandwiched between the negative electrodes having about half the capacity of the positive electrode.

  In the lithium ion secondary battery of the present invention, the separator has a porosity of 30% or more and 90% or less, and the separator has a thickness of 5 μm or more and 100 μm or less.

In such a lithium ion secondary battery, the internal resistance increases in the lithium ion secondary battery porosity reduces the content of the non-aqueous electrolyte than the low Kunar 30% of the separator. Further, the higher due the positive electrode and the negative electrode porosity than 90% of the separator will undergo physical contact, internal short circuit of the lithium ion secondary battery may occur. Further, when the thickness of the separator is thinner than 5 [mu] m, therefore, the mechanical strength of the separator is insufficient, causing an internal short circuit of the lithium ion secondary battery. Further, the thickness of the separator is thicker than 100 [mu] m, therefore, the distance between the positive electrode negative electrode is increased, the internal resistance of the lithium ion secondary battery is higher due. The separator can be selected from non-woven fabric and microporous membrane made of polyethylene, polypropylene, polyester, etc., but when the separator is non-woven fabric made of polyester, the non-woven fabric is more than the microporous membrane. The non-aqueous electrolyte containing the γ-butyrolactone is more permeable and more suitable.

  In the lithium ion secondary battery of the present invention, the salt concentration of the electrolyte salt dissolved in the non-aqueous electrolyte is 0.5 mol / l or more and 3 mol / l or less.

In such a lithium ion secondary battery, the salt concentration of the non-aqueous electrolyte, the carrier concentration of the electrolyte solution to be below 0.5 mol / l is low, the resistance of the nonaqueous electrolyte solution is increased. Moreover, the salt concentration of the nonaqueous electrolyte solution is lower higher due salt dissociation degree itself than 3 mol / l, the carrier concentration of the non-aqueous electrolyte can not rise.

  In the lithium ion secondary battery of the present invention, the pore size of the porous metal body constituting the current collector is 1 mm or less, and the porosity of the current collector is 50% or more and 98%. It is characterized by the following.

In such a lithium ion secondary battery, the size Kunar than magnitude 1mm of pores of the metal porous body constituting the current collector, the air of the positive electrode active material and the current collector from the anode active material distance to the hole inner wall is increased, as a result, resistance increases. On the contrary, when the size of the pores of the metal porous body is 1 mm or less, the possibility that the positive electrode active material or the negative electrode active material in the pores is detached from the pores of the metal porous body is reduced. preferable. Furthermore, the porosity of the current collector, air porosity can not be low Kunar and the active material is sufficiently filled than 50%, invited rather a decrease in energy density of the lithium ion secondary battery. Conversely, porosity strength higher due to the electrode becomes weaker than 98%, also, the effect of heat dissipation can not be obtained sufficiently.

  In the lithium ion secondary battery of the present invention, the negative electrode has a porosity of 30% or more and 90% or less.

  In such a lithium ion secondary battery, the negative electrode active material is mixed with a binder or the like in a three-dimensional porous metal body and pasted into a paste, and then the porous metal body is pressed to form the negative electrode. To do. In the negative electrode, when a graphite-based material is used as the negative electrode active material and the γ-butyrolactone is contained in the non-aqueous electrolyte, the permeability of the non-aqueous electrolyte into the negative electrode is reduced. The discharge characteristics, charge / discharge cycle characteristics, and low temperature characteristics of the lithium ion secondary battery are deteriorated. For this reason, in order to suppress these problems, it is preferable that voids exist in the negative electrode with a porosity in the above range.

  In the lithium ion secondary battery of the present invention, the negative electrode active material is a mixture of graphite powder and carbon fiber powder.

  In order to further improve the problem that the non-aqueous electrolyte permeability to the negative electrode is lowered when the γ-butyrolactone is used as the non-aqueous electrolyte solvent described above, the negative electrode active material is used as a graphite powder. Carbon fiber powder is used as a mixture. In particular, natural graphite powder has a scaly shape, and there is a problem that the natural graphite powder is oriented inside the electrode and the voids are reduced. In such a lithium ion secondary battery, the decrease in the voids of the negative electrode is suppressed by mixing the carbon fiber powder having a shape different from that of the natural graphite, and the carbon fiber powder is also used as the negative electrode active material. It contributes and capacity loss can be suppressed.

  In the lithium ion secondary battery of the present invention, the negative electrode active material includes graphite having good crystallinity.

  As a negative electrode active material for lithium ion secondary batteries, carbonaceous materials have been widely used. In particular, in view of flatness of charge / discharge potential, high charge / discharge efficiency, etc., a highly crystalline graphite material. Is preferred. As the graphite material having such high crystallinity, for example, natural graphite may be used. This natural graphite not only has a large amount of reserves worldwide, but also has higher crystallinity than artificial graphite, and is therefore suitable as the negative electrode active material of the present invention.

  In the lithium ion secondary battery of the present invention, the negative electrode active material includes vapor grown carbon fibers.

  Vapor grown carbon fibers (hereinafter referred to as VGCF) are used as the carbon fibers used in the negative electrode active material, and VGCF has the same high crystallinity as natural graphite while being in the shape of carbon fibers. In addition, since it is possible to achieve both the flatness of the charge / discharge potential, the high charge / discharge efficiency, and the effect of suppressing the decrease in the gap of the negative electrode, it is suitable as the negative electrode active material of the present invention.

  With the configuration of the present invention, the performance of the large-sized lithium ion secondary battery is excellent and the safety can be improved.

According to the present invention, the positive electrode active material is not only compatible with the conflicting elements of high potential / high energy density and high safety / stability, but is also a material that realizes a low environmental load mainly composed of iron. Some olivine type LiFePO ₄ is used. In addition, a three-dimensional metal porous body having a plurality of holes is used as a current collector constituting the electrode. In addition, γ-butyrolactone has the properties of having both high dielectric constant and low viscosity, excellent oxidation resistance, high boiling point, low vapor pressure, high flash point, etc. Heat generation when stored at high temperature or overcharged by making the content of γ-butyrolactone contained in the non-aqueous electrolyte to be 50% or more and 80% or less in volume fraction. Less volume and less gas generation. Therefore, safety can be increased as compared with a lithium ion secondary battery as a conventional power source for portable devices.

Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view of the lithium ion secondary battery of the present embodiment. The lithium ion secondary battery includes a positive electrode active material 1 and a negative electrode active material 2 that are mixed with a binder, a conductive material, and the like (not shown) to form a paste-like material, and a porous metal such as a sponge. Current collectors 3a and 3b, and separator 4 provided between current collectors 3a and 3b so that the positive electrode side and the negative electrode side are not in direct contact with each other, and current collectors 3a and 3b and the separator 4 and a nonaqueous electrolytic solution 6 in which an electrolyte salt (not shown) such as lithium borofluoride (LiBF ₄ ) is dissolved.

  In such a lithium ion secondary battery, the positive electrode active material 1 is applied to the current collector 3a to form the positive electrode, and the negative electrode active material 2 is applied to the current collector 3b to form the negative electrode. . By providing the separator 4 between the current collectors 3a and 3b, the positive electrode side and the negative electrode side are in direct contact with each other, thereby preventing a short circuit. During charging, lithium ions escape from the positive electrode side and move to the negative electrode, and during discharging, lithium ions escape from the negative electrode side and return to the positive electrode side. That is, the charge / discharge operation is performed by the movement of lithium ions between the positive electrode and the negative electrode.

  Details of the lithium ion secondary battery configured as shown in FIG. 1 will be described below. First, when such a lithium ion secondary battery is used in a system that requires a large capacity, such as a household distributed power source and a power storage system of a photovoltaic power generation system, it is necessary to use an assembled battery to obtain a large capacity. There is. However, when a small lithium ion secondary battery having a small charge / discharge capacity is used as a single battery, hundreds to thousands of single cells are required, and maintenance of the power storage system becomes very complicated. For this reason, the lithium ion secondary battery is large in size with a large charge / discharge capacity, and preferably the charge / discharge capacity as a single battery is 5 Ah or more.

At this time, when the electric capacity per cm ² is less than 10 mAh in the positive electrode composed of the positive electrode active material 1 and the current collector 3a and the negative electrode composed of the negative electrode active material 2 and the current collector 3b. The number of stacked layers per unit cell becomes ten to several tens, and the unit cell manufacturing operation becomes complicated. For this reason, the electric capacity per 1 cm < ² > of a positive electrode and a negative electrode shall be 10 mAh or more. The configuration of the lithium ion secondary battery having such a capacity value will be described below.

(Positive electrode and negative electrode)
First, when the thickness of the positive electrode and the negative electrode is 10 mm or more, the electrolyte does not sufficiently permeate and it is difficult to maintain the performance. On the other hand, when the thickness of the electrode is smaller than 1 mm, the porosity inside the electrode is lowered, and the weight of the electrode active material is reduced, resulting in an increase in the number of stacked layers. Therefore, in the present embodiment, the thickness of the positive electrode and the negative electrode is 1 mm or more and less than 10 mm, although it depends on the density of the active material, the binder to be mixed, the type of the conductive material, the press pressure of the electrode, and the like.

  Further, regarding the thickness of the positive electrode and the negative electrode used in the present embodiment, it is preferable to increase the thickness of the positive electrode when either one of the electrodes is a thick electrode. This is because in a lithium ion secondary battery, the negative electrode is charged and discharged at a potential close to that of lithium metal, and therefore lithium may be deposited when the polarization of the negative electrode increases. Further, as described later, by increasing the thickness of the positive electrode, a structure in which the negative electrode is disposed on both sides of the positive electrode can be adopted, and the polarization of the negative electrode can be reduced, so that lithium deposition can be avoided. In this case, the thick positive electrode is sandwiched between the negative electrodes having about half the capacity of the positive electrode (see FIG. 3).

Moreover, as for the positive electrode material such as LiCoO ₂ which has been used for the positive electrode so far, the oxygen is released as the temperature rises, and the electrolyte solution burns to generate intense heat. Moreover, LiCoO ₂ containing cobalt (Co) has a problem that it is difficult to keep using Co because Co is less in comparison with iron (Fe) and Mn (manganese). In recent years, attention has been paid to olivine-type LiFePO ₄ containing iron as a main component as a low environmental load / ultra-low cost positive electrode material. This LiFePO ₄ not only achieves both high potential / high energy density and high safety / stability, but also contains iron as a main component and has a low environmental load. In addition, since all the oxygen in LiFePO ₄ is bonded to phosphorus by a strong covalent bond, there is no heat generation as in other positive electrode materials such as LiCoO ₂ described above, and oxygen is not easily released due to temperature rise. From the viewpoint of safety. Moreover, since it contains phosphorus, the positive electrode generates heat, and even when the electrolyte leaks, it can be expected to have an anti-flame effect, which is preferable. For this reason, the positive electrode of the present embodiment uses olivine type LiFePO ₄ as the positive electrode active material 1.

As described above, the lithium ion secondary battery using olivine-type LiFePO ₄ as the positive electrode active material 1 has a charging voltage of about 3.5 V, and is almost completely charged at 3.8 V, which causes decomposition of the electrolytic solution. There is a margin to the voltage of about 4.5V. In addition, when the positive electrode material whose charging voltage reaches 4.0 V or higher is used for the positive electrode active material 1, it is not preferable because the electrolyte solution is easily decomposed when the charging voltage is further increased.

  In addition, the safety of large batteries greatly depends on the heat generation behavior and the heat dissipation rate. In a large-sized lithium ion secondary battery, since the battery size is large, heat tends to accumulate inside. However, when a metal three-dimensional structure is used for the current collectors 3a and 3b constituting the electrode, the metal having excellent thermal conductivity is uniformly present throughout the entire electrode within the lithium ion secondary electrode, so that It becomes possible to improve the heat dissipation of. For this reason, in this embodiment, the current collectors 3a and 3b are made of a porous metal body that is three-dimensionally connected. This makes it possible to further improve safety.

  Further, in the pores of the three-dimensional metal porous body used for the current collectors 3a and 3b described above, if the size is larger than 1 mm, the distance from the active material to the pore inner walls of the current collectors 3a and 3b As a result, the resistance increases. Furthermore, it is preferable that the pores of the metal porous body have a size of 1 mm or less because the possibility that the positive electrode active material 1 or the negative electrode active material 2 in the pores will deviate from the pores of the metal porous body is reduced. Therefore, in this embodiment, the size of the three-dimensionally connected metal porous body used for each of the current collectors 3a and 3b is set to 1 mm or less, more preferably 0.5 mm or less.

  Furthermore, when the porosity of the metal porous body described above is low, the active material cannot be sufficiently filled, resulting in a decrease in the energy density of the lithium ion secondary battery. Also, when the porosity is high, the strength of the electrode becomes weak and the effect of heat dissipation cannot be obtained sufficiently. For this reason, in this embodiment, the porosity of a metal porous body shall be 50% or more and 98% or less, More preferably, you may be 75% or more and 98% or less.

  Unlike the electrodes applied to the metal foil as in the prior art, the electrodes using such a three-dimensionally connected metal porous body as the current collectors 3a and 3b can pass ions from the back to the front. It becomes. Therefore, by arranging the counter electrodes on both sides, ions are supplied from both sides, so that the cycle characteristics are also improved.

  After the negative electrode active material 2 is mixed with a binder or the like in a three-dimensionally connected metal porous body and pasted and filled, the metal porous body is pressed to form a negative electrode. In this negative electrode, when a graphite-based material is used as the negative electrode active material 2, if the non-aqueous electrolyte 6 contains γ-butyrolactone, which will be described later, the permeability of the non-aqueous electrolyte 6 to the negative electrode is lowered. The discharge characteristics, charge / discharge cycle characteristics, and low temperature characteristics of the lithium ion secondary battery are deteriorated. For this reason, in order to suppress these problems, it is preferable that a void exists inside the negative electrode. For this reason, in this embodiment, the porosity of a negative electrode shall be 30% or more and 90% or less.

  Since the electrodes using the above-described three-dimensional structure as the current collectors 3a and 3b are arranged with a metal having a high three-dimensional thermal conductivity, it is possible to keep the temperature inside the electrode uniform and large. It is possible to suppress cycle deterioration caused by a local temperature rise that becomes a problem in the case of a lithium ion secondary battery. In the electrode used in this embodiment, metal fibers may be dispersed in the positive electrode active material 1 or the negative electrode active material 2 in order to improve conductivity between the active materials and heat dissipation. The length of the metal fiber is preferably about the same as the size of the gap of the three-dimensional structure used as the current collectors 3a and 3b.

  The “three-dimensional metal porous body” refers to a sponge-like metal structure, a non-woven fabric made of metal fibers, a sintered metal powder, a metal foil molded into a honeycomb structure, and the like. Moreover, the material of the metal porous body used for each of these current collectors 3a and 3b is not particularly limited, but aluminum, titanium, stainless steel, etc. have oxidation resistance as materials used for the current collector 3a for the positive electrode. It is preferable because it is high, and copper, nickel, iron, stainless steel, and the like are preferable for the material used for the current collector 3b for the negative electrode because it is difficult to alloy with lithium and has high electrical conductivity.

(Nonaqueous electrolyte)
γ-Butyrolactone (GBL) has the properties of having both a high dielectric constant and a low viscosity, and also has excellent oxidation resistance, high boiling point, low vapor pressure, and high flash point. For this reason, when used in non-aqueous electrolytes, the amount of heat generated when stored at high temperatures or overcharged is small, and the amount of gas generated is also small, which is very high compared to conventional small lithium ion secondary batteries. It is suitable as a solvent for an electrolytic solution of a large lithium ion secondary battery that requires safety. For this reason, it is assumed that the non-aqueous electrolyte 6 used in the present embodiment contains GBL.

  In the non-aqueous electrolyte 6, solvents that can be used by mixing with GBL include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate, dimethyl carbonate (DMC), diethyl carbonate ( DEC), chain carbonates such as ethylmethyl carbonate and dipropyl carbonate, lactones such as γ-valerolactone, furans such as tetrahydrofuran and 2-methyltetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, 1,2 -Ethers such as diethoxyethane, ethoxymethoxyethane, dioxane and the like, dimethyl sulfoxide, sulfolane, methyl sulfolane, acetonitrile, methyl formate, methyl acetate, etc. may be mentioned. It does not. In particular, cyclic carbonates such as PC, EC and butylene carbonate are preferred because they are high-boiling solvents.

  Further, regarding the GBL content in the non-aqueous electrolyte 6, if the GBL content is less than 50% in terms of volume fraction, the safety of the large-sized lithium ion secondary battery is lowered. Further, when the content of GBL is more than 80%, the permeability of the electrolytic solution to not only the electrode but also other members constituting the lithium ion secondary battery, such as a separator, is reduced, and the lithium ion secondary battery is reduced. The performance of is reduced. For this reason, in the nonaqueous electrolytic solution 6 of the lithium ion secondary battery of the present embodiment, the content rate of GBL in the solvent for the nonaqueous electrolytic solution is 50% or more and 80% or less. As the nonaqueous electrolytic solution 6, a gel electrolyte in which an electrolytic solution composed of the above solvent is held in a polymer matrix may be used.

Also, electrolyte salts dissolved in the non-aqueous electrolyte 6 include lithium borofluoride (LiBF ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), trifluoro Examples thereof include lithium salts such as lithium acetate (LiCF ₃ COO) and lithium bis (trifluoromethanesulfone) imide (LiN (CF ₃ SO ₂ ) ₂ ), and one or more of these may be mixed and used.

  When the salt concentration of the non-aqueous electrolyte 6 described above is 0.5 mol / l or less, the carrier concentration in the electrolyte is decreased, and thus the resistance of the non-aqueous electrolyte 6 is increased. On the other hand, if the salt concentration of the non-aqueous electrolyte 6 is higher than 3 mol / l, the dissociation degree of the salt itself is lowered, and the carrier concentration in the non-aqueous electrolyte 6 does not increase. For this reason, the salt concentration of the nonaqueous electrolytic solution 6 in the present embodiment is set to 0.5 to 3 mol / l.

(Separator)
The separator 4 used in the present embodiment can be selected from a nonwoven fabric made of polyethylene, polypropylene, polyester, or the like, or a microporous membrane. When the separator 4 is a nonwoven fabric made of polyester, the nonwoven fabric is fine. The nonaqueous electrolytic solution 6 containing GBL is higher in permeability than the porous membrane, and is more preferable.

  For the separator 4 described above, when the porosity is lower than 30%, the content of the non-aqueous electrolyte 6 is reduced and the internal resistance of the lithium ion secondary battery is increased. When the porosity is higher than 90%, the positive electrode and the negative electrode are physically separated. Contact is caused, which causes an internal short circuit of the lithium ion secondary battery. Further, when the thickness of the separator 4 is less than 5 μm, the mechanical strength of the separator 4 is insufficient, causing an internal short circuit of the lithium ion secondary battery. When the thickness is greater than 100 μm, the distance between the positive electrode and the negative electrode is increased. The internal resistance of the secondary battery increases. For this reason, in this embodiment, the porosity of the separator 4 is 30% or more and 90% or less, and the thickness of the separator 4 is 5 μm or more and 100 μm or less.

(Exterior material)
Further, the outer packaging material 5 of the lithium ion secondary battery used in the present embodiment is preferably a metal can such as a can made of iron, stainless steel, aluminum, or the like. Moreover, you may use the film-form bag which laminated the ultra-thin aluminum with resin. The shape of the exterior material 5 may be any of a cylindrical shape, a rectangular shape, a thin shape, and the like. However, since a large-sized lithium ion secondary battery has many opportunities to be used as an assembled battery, the rectangular shape or the thin shape is preferable.

  The lithium ion secondary battery according to the embodiment of the present invention has a configuration as shown in FIG. 1, but has a configuration in which separators 4a and 4b are provided between current collectors 3a and 3b as shown in FIG. It doesn't matter. In addition, as shown in FIG. 3, two negative electrodes each including the negative electrode active material 2 and the current collector 3 b and two separators 4 may be provided.

  Hereinafter, Examples 1 to 3 of the lithium ion secondary battery manufactured according to the present embodiment and evaluation results in each example will be described. The configuration of Example 1 is as shown in FIG. 1, the configuration of Example 2 is as shown in FIG. 2, and the configuration of Example 3 is as shown in FIG.

An olivine type LiFePO ₄ is used for the positive electrode active material 1, 20 parts by weight of acetylene black as a conductive material, 10 parts by weight of PVdF as a binder, and NMP is used as a solvent to prepare a positive electrode paste. The obtained paste was filled in foamed aluminum (size: 10 cm × 20 cm, thickness 4 mm, porosity 92%) used as the current collector 3a, dried sufficiently, and then pressed using a hydraulic press to obtain a thickness. A 3.0 mm electrode is obtained. The active material weight per area of the electrode thus obtained was 210 mg / cm ² and the porosity of the positive electrode was 55%.

The negative electrode active material 2 includes Chinese natural graphite powder (average particle size 15 μm, d002 = 0.3357 nm, BET specific surface area 3 m ² / g) and VGCF powder (average particle size 15 μm, d002 = 0.3359 nm, BET ratio). Using a mixture of a surface area of 2 m ² / g) at a weight ratio of 50:50, 12 parts by weight of PVdF is added as a binder, and NMP is used as a solvent to prepare a negative electrode paste. The obtained paste was filled into a non-woven fabric of copper fibers (size: 10.2 cm × 20.2 cm, thickness 2.5 mm, porosity 88%) used as the current collector 3b, and after sufficiently drying, a hydraulic press was used. And press to obtain an electrode having a thickness of 1.5 mm. The active material amount per area of the electrode thus obtained was 95 mg / cm ² and the porosity of the negative electrode was 50%.

  Moreover, a polyester nonwoven fabric having a thickness of 50 μm is used as the separator 4, and the electrodes obtained by the above-described method are laminated so that one positive electrode and one negative electrode face each other, and are inserted into a bag-like aluminum laminate. did.

The non-aqueous electrolyte 6 uses a solution in which LiBF ₄ is dissolved in a solvent in which GBL and EC are mixed at a volume ratio of 7: 3 so that the concentration is 1.5 mol / l. The laminate was inserted into an aluminum laminating bag, and the electrolyte solution was poured and sealed by thermal fusion to produce a lithium ion secondary battery with a design capacity of 5 Ah according to this example. The lithium ion secondary battery thus produced was tested. This test and test results will be described later.

  Since the positive electrode is the same as in Example 1, detailed description thereof will be omitted with reference to Example 1.

The negative electrode active material 2 includes natural graphite powder from China (average particle size 15 μm, d002 = 0.3357 nm, BET specific surface area 3 m ² / g) and PAN (polyacrylonitrile) -based carbon fiber powder (average particle size 15 μm, d002). = 0.3400 nm, BET specific surface area 3 m ² / g) mixed at a weight ratio of 80:20, 6 parts by weight of latex rubber as a binder, and CMC (carboxymethylcellulose) -NH ₄ as a thickener. 6 parts by weight is added and dissolved and dispersed in water to prepare a negative electrode paste. The obtained paste was filled in foamed nickel (size: 10.2 cm × 20.2 cm, thickness 2.5 mm, porosity 90%) used as the current collector 3b, dried sufficiently, and then pressed using a hydraulic press. Thus, an electrode having a thickness of 1.8 mm is obtained. The active material amount per area of the electrode thus obtained was 99 mg / cm ² and the porosity of the negative electrode was 60%.

  In addition, two non-woven fabrics made of polyethylene having a thickness of 25 μm are used as separators 4a and 4b (see FIG. 2), and the obtained electrodes are laminated so that one positive electrode and one negative electrode face each other, and a bag-like aluminum Inserted into the laminate.

The non-aqueous electrolyte 6 was prepared by dissolving LiBF ₄ in a solvent in which GBL and EC were mixed at a volume ratio of 5: 5 so that the concentration was 1.7 mol / l. The laminate was inserted into an aluminum laminating bag, and the electrolyte solution was poured and sealed by thermal fusion to produce a lithium ion secondary battery with a design capacity of 5 Ah according to this example. The lithium ion secondary battery thus produced was tested in the same manner as in Example 1. This test and test results will be described later in the same manner as in Example 1.

  Below, the evaluation result of the lithium ion secondary battery produced by this embodiment is demonstrated. Since the positive electrode is the same as in Example 1, detailed description thereof will be omitted with reference to Example 1.

Artificial graphite powder (average particle size 12 μm, d002 = 0.3365 nm, BET specific surface area 7 m ² / g) is used for the negative electrode active material 2, 4 parts by weight of latex rubber as a binder, and CMC-NH as a thickener. ₄ 4 parts by weight were added and dissolved in the water-dispersed to prepare a negative electrode paste. The obtained paste was filled in foamed nickel (size: 10.2 cm × 20.2 cm, thickness: 1.4 mm, porosity: 95%) used as the current collector 3b, dried sufficiently, and then pressed using a hydraulic press. Then, two electrodes having a thickness of 1.1 mm are obtained. The active material amount per area of the electrode thus obtained was 45 mg / cm ² and the porosity of the negative electrode was 70%.

  Further, two polypropylene non-woven fabrics coated with a surfactant on the surface having a thickness of 25 μm are used as the separator 4, and one positive electrode obtained as shown in FIG. 3 is sandwiched between two negative electrodes and laminated. Inserted into a shaped aluminum laminate.

The non-aqueous electrolyte 6 is prepared by dissolving LiBF ₄ in a solvent in which GBL and DEC are mixed at a volume ratio of 5: 5 so that the concentration is 1.2 mol / l. The laminate was inserted into an aluminum laminating bag, and the electrolyte solution was poured and sealed by thermal fusion to produce a lithium ion secondary battery with a design capacity of 5 Ah according to this example. The lithium ion secondary battery thus produced was tested in the same manner as in Example 1. This test and test results will be described later in the same manner as in Examples 1 and 2.

  Each of the lithium ion secondary batteries obtained in Examples 1 to 3 was subjected to a charge / discharge test under the following conditions. Regarding charging, charging is performed until the charging current is 1.5 A and the voltage is 4.2 V, and then the charging is terminated when 15 hours elapses at the voltage 4.2 V or when the charging current is 0.1 A. About discharge, it discharges until a discharge current is 1.5A and a voltage becomes 2.75V. After charging and discharging 100 times under these conditions, the battery capacity of the fully charged lithium ion secondary battery charged to the full capacity at that time is measured, and the lithium ion secondary battery is laid down side by side. In this state, a nail penetration test for penetrating a 2.5 mmφ nail was performed. The result is shown in FIG.

4 and 5, the lithium ion secondary battery of the present invention using olivine-type LiFePO _{4 as the} positive electrode active material 1 and GBL as the non-aqueous electrolyte 6 is subjected to a nail penetration test. Even if it is implemented, no white smoke or the like is generated, and no abnormal heat is generated inside, so that the safety is improved from the lithium ion secondary battery according to the prior art. Moreover, when the evaluation results of Example 1 and Example 2 are compared, it can be seen that Example 1 in which VGCF is mixed with negative electrode active material 2 has a smaller decrease in battery capacity and excellent cycle characteristics. Similarly, when Example 1 is compared with Example 3, Example 1 in which VGCF powder is mixed with the negative electrode active material 2 has better cycle characteristics, and natural graphite is used for the negative electrode active material 2. It can be seen that Example 1 and Example 2 have better cycle characteristics than Example 3 using artificial graphite. Furthermore, when Example 3 is compared with Example 1 or Example 2, the surface maximum temperature of Example 3 is low. Thus, Example 3 having a structure in which a positive electrode is sandwiched between two negative electrodes is more than Example 1 and Example 2 having a structure in which an electrode is laminated so that one positive electrode and one negative electrode face each other. It can be seen that the heat diffusion efficiency is high.

It is a schematic sectional drawing which shows the structure of the lithium ion secondary battery of this invention. It is a schematic sectional drawing which shows the structure of the modification of the lithium ion secondary battery of this invention. It is a schematic sectional drawing which shows the structure of the modification of the lithium ion secondary battery of this invention. It is a figure which shows the test result of the lithium ion secondary battery in Example 1, Example 2, and Example 3 of this invention. It is a figure which shows the test result of the lithium ion secondary battery by a prior art.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Positive electrode active material 2 Negative electrode active material 3a Current collector 3b Current collector 4 Separator 4a Separator 4b Separator 5 Exterior material 6 Nonaqueous electrolyte

Claims (10)

A positive electrode comprising a current collector having a positive electrode active material, a negative electrode comprising a current collector having a negative electrode active material, a separator, a lithium ion secondary battery comprising a non-water electrolytic solution, a containing lithium salt There,
The battery capacity is 5 Ah or more and the electric capacity per 1 cm ^{2 of the} positive electrode and the negative electrode is 10 mAh or more,
The positive electrode active material is olivine type LiFePO ₄ ;
The current collector is a three-dimensional porous metal body having a plurality of pores;
The non-aqueous electrolyte contains at least γ-butyrolactone ,
The non-aqueous content of the γ- butyrolactone contained in the electrolytic solution, the lithium ion secondary battery, characterized der Rukoto 80% 50% or more or less at a volume fraction. The lithium ion secondary battery according to claim 1, wherein the thickness of at least one of the positive electrode and the negative electrode is 1 mm or more and less than 10 mm. While comprising a plurality of the negative electrode and the separator,
Lithium-ion secondary battery according to claim 1 or claim 2, characterized in placing the negative electrode on both sides of the positive electrode so as to sandwich the positive electrode through the separator. Porosity of the separator is, along with 90% or less than 30%, a lithium ion secondary according to any one of claims 1 to 3, the thickness of the separator is equal to or is 5μm or more 100μm or less Next battery. Lithium-ion secondary battery according to any one of claims 1 to 4 salt concentration of the lithium salt dissolved in the nonaqueous electrolytic solution is equal to or less than 0.5 mol / l or more 3 mol / l . The pore size of the metal porous body constituting the current collector is 1 mm or less, and the porosity of the current collector is 50% or more and 98% or less . The lithium ion secondary battery according to claim 5 . Lithium-ion secondary battery according to any one of claims 1 to 6, wherein the porosity of the negative electrode is 30% or less than 90%. The lithium ion secondary battery according to any one of claims 1 to 7 , wherein the negative electrode active material is a mixture of graphite powder and carbon fiber powder. The lithium ion secondary battery according to any one of claims 1 to 8 , wherein the negative electrode active material includes graphite having good crystallinity. The lithium ion secondary battery according to any one of claims 1 to 9 , wherein the negative electrode active material includes vapor-grown carbon fibers.

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