JP5708121B2 - Secondary battery gas ejection prevention material, gas ejection prevention system, and secondary battery system using the same - Google Patents

Description

  The present invention relates to a gas ejection preventing material having a function of preventing the gas generated inside the battery or the electrolyte vapor from being ejected to the outside when the secondary battery is abnormal, a gas ejection preventing system including the gas ejection preventing material, and The present invention relates to a secondary battery system using this gas ejection prevention system.

  In a non-aqueous electrolyte secondary battery such as a lithium ion battery, the internal temperature rises due to the gas generated by evaporation or decomposition of the electrolyte when an overcharge or short circuit occurs, resulting in a battery case. There is a risk of damage. Therefore, the non-aqueous electrolyte secondary battery is equipped with an explosion-proof valve, and in the unlikely event that the specified internal pressure is exceeded, the electrolyte vapor or other decomposition gas is ejected from the explosion-proof valve to the outside. Yes. However, since these gases contain a large amount of flammable or toxic substances, various ejection prevention techniques that do not eject these gases to the outside have been developed.

  As this ejection prevention technique, for example, Patent Document 1 discloses a technique in which a gas generated inside a laminate-type lithium ion battery is absorbed by a gas adsorbent to prevent the laminate film from expanding. Further, in Patent Document 2, by providing a gas absorption element including a gas ejection preventing material inside the secondary battery, it is possible to prevent the ejection of gas or the like by stably suppressing an increase in the internal pressure of the battery for a long period of time. Technology is disclosed.

  Further, Patent Document 3 proposes to provide a filter as a battery safety valve in order to prevent solid matter inside the battery from scattering when the safety valve is opened due to an increase in internal pressure due to gas generation inside the battery. Yes.

JP 2001-155790 A Japanese Patent Laid-Open No. 2003-77549 JP-A-7-192712

  However, when the safety valve is opened, the inside of the battery is very hot, and both the speed and pressure of the gas to be ejected are very high, so that conventional gas ejection as described in Patent Document 1 and Patent Document 2 is performed. There is a problem that the performance of the preventive material is insufficient. In particular, there is no effective adsorbent for harmful carbon monoxide generated by decomposition of the electrolyte. Therefore, it is conceivable to decompose with a catalyst or the like, but there are problems such as that it is necessary to set a predetermined temperature for the decomposition and that it is not suitable for decomposing a high concentration of carbon monoxide, which is not practical. Furthermore, the filter as described in Patent Document 3 has a problem that a gas component collecting effect cannot be expected so much.

  In addition, non-aqueous electrolyte secondary batteries are often applied to devices with limited installation space, such as mobile devices and automobiles. Therefore, in addition to high gas absorption performance, they must be compact and low-cost. Is done.

  The present invention has been made in view of the above problems, and a secondary battery gas ejection preventing material capable of efficiently absorbing the electrolytic solution decomposition gas ejected from the nonaqueous electrolyte secondary battery in a space-saving manner at low cost. The purpose is to provide. Another object of the present invention is to provide a gas ejection preventing system using the gas ejection preventing material and a secondary battery system using the same.

  In order to solve the above-mentioned problems, firstly, the present invention includes a casing in which a positive electrode and a negative electrode are sealed together with an electrolyte solution, an explosion-proof valve for releasing high-pressure gas inside the casing when the internal pressure of the casing increases. A secondary battery gas ejection preventing material for absorbing gas ejected in the event of an abnormality in a secondary battery comprising a secondary battery comprising an inorganic porous material mainly composed of silicon dioxide and aluminum oxide A gas ejection preventing material for a battery is provided (Invention 1).

  According to this invention (Invention 1), the inorganic porous material mainly composed of silicon dioxide and aluminum oxide absorbs hydrocarbon gases such as carbon monoxide, methane, and ethane quickly and with a high absorption rate. It is possible to prevent these gas components from being ejected from the explosion-proof valve when the secondary battery is abnormal. In addition, since the amount of the gas ejection preventing material is small, the secondary battery system can be made compact.

  In the said invention (invention 1), it is preferable that the said inorganic porous raw material has an element composition ratio of the range of Si / Al ratio 2-5 (invention 2). The inorganic porous material is preferably A-type or X-type zeolite (Invention 3).

  According to such inventions (Inventions 2 and 3), it is possible to absorb the electrolyte vapor, other decomposition gas, and the like more quickly and with a high absorption rate.

  In the said invention (invention 1), it is preferable that the said inorganic porous material contains lithium (invention 4). Moreover, it is preferable that the lithium content rate of the said inorganic porous material is 1-20 mass% (invention 5). The inorganic porous material preferably has an elemental composition ratio in a range of Si / Al ratio of 1 to 2.4 (Invention 6).

  According to such inventions (Inventions 4 to 6), the vapor of the electrolytic solution of the electrolytic solution and other decomposition gases, particularly low molecular weight gas components such as carbon monoxide and methane gas are absorbed more quickly and with a high absorption rate. be able to.

  In the said invention (invention 1-6), it is preferable that the said inorganic porous material has a pore diameter of 3 to 10 inches (invention 7).

  According to this invention (invention 7), carbon monoxide, hydrocarbon gas, etc. can be trapped in the pores and these gases can be absorbed more rapidly.

In the said invention (invention 1-7), it is preferable that the said inorganic porous raw material has a specific surface area of 100-1000 m < ² > / g (invention 8).

  According to this invention (invention 7), a sufficient contact area between the inorganic porous material and a gas component such as carbon monoxide or hydrocarbon gas can be secured, so that a high absorption rate can be maintained.

  In the said invention (invention 1-8), it is preferable that the said inorganic porous raw material has an average particle diameter of 100-2000 micrometers (invention 9). The inorganic porous material is preferably a powder molded product (Invention 10).

  According to the inventions (Inventions 9 and 10), the contact efficiency between the inorganic porous material and the ejected carbon monoxide, hydrocarbon gas, or the like can be improved, so that the ejection prevention effect is maintained at a high level. can do.

  In the said invention (invention 1-8), it is preferable that the said inorganic porous raw material has an average particle diameter of 100-2000 micrometers (invention 9). The inorganic porous material is preferably a powder molded product (Invention 10).

  Secondly, the present invention provides a gas ejection preventing system using the gas ejection preventing material according to any one of the inventions 1 to 10 (invention 11).

  According to this invention (Invention 11), the inorganic porous material mainly composed of silicon dioxide and aluminum oxide is combustible such as ethylene carbonate, ethyl methyl carbonate, or dimethyl carbonate enclosed in the casing of the secondary battery. Because it absorbs the electrolyte vapor and other decomposition gas of the electrolyte quickly and with a high absorption rate, it prevents the electrolyte vapor from blowing out from the explosion-proof valve when the secondary battery is abnormal be able to.

  Thirdly, the present invention provides a secondary battery system comprising the gas ejection prevention system according to the eleventh aspect (Invention 12).

  According to this invention (Invention 12), the inorganic porous material mainly composed of silicon dioxide and aluminum oxide absorbs hydrocarbon gases such as carbon monoxide, methane, and ethane quickly and with a high absorption rate. These gas components can be prevented from being ejected from the explosion-proof valve when the secondary battery is abnormal, and the high-pressure gas ejected from the plurality of secondary batteries can be suitably absorbed. In addition, since the amount of the gas ejection preventing material is small, the secondary battery system can be made compact.

  According to the present invention, a secondary battery is ejected when an abnormality occurs in a secondary battery including a housing in which a positive electrode and a negative electrode are sealed together with an electrolyte, and an explosion-proof valve for releasing high-pressure gas inside the housing when the internal pressure of the housing increases. As a gas blowout prevention material that absorbs the generated gas, a material composed of an inorganic porous material mainly composed of silicon dioxide and aluminum oxide is used, so that hydrocarbon gases such as carbon monoxide, methane, and ethane can be absorbed quickly and with high absorption. The gas component can be absorbed at a high rate, and the gas components can be prevented from being ejected from the explosion-proof valve when the secondary battery is abnormal. In addition, since the amount of the gas ejection preventing material is small, the secondary battery system can be made compact. In particular, when the inorganic porous material contains lithium, gas components having a low molecular weight such as carbon monoxide and methane gas can be absorbed more quickly and with a high absorption rate.

1 is a perspective view showing a nonaqueous electrolyte secondary battery according to an embodiment of the present invention. It is sectional drawing which shows roughly the internal structure of the nonaqueous electrolyte secondary battery which concerns on one Embodiment of this invention. It is a flowchart which shows the test apparatus of a gas ejection prevention material.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, each embodiment is only an example, and the present invention is not limited to this.

  1 and 2 show a non-aqueous electrolyte secondary battery to which the gas ejection preventing material of this embodiment can be applied. 1 and 2, a nonaqueous electrolyte secondary battery E such as a lithium ion battery is formed on a positive electrode terminal 1 and a negative electrode terminal 2, a battery case (housing) 3, and an outer peripheral surface of the battery case 3. And an explosion-proof valve 4, and the electrode body 10 is housed inside the battery case 3. As shown in FIG. 2, the electrode body 10 includes a positive electrode current collector 11 and a positive electrode plate 12, and a negative electrode current collector 13 and a negative electrode plate 14. The positive electrode plate 12 and the negative electrode plate 14 each have a structure wound around a separator 15. The positive terminal 1 is electrically connected to the positive electrode plate 12, and the negative terminal 2 is electrically connected to the negative electrode plate 14. The battery case 3 as a housing is, for example, a square battery tank can made of aluminum or stainless steel.

  In such a non-aqueous electrolyte type secondary battery, the explosion-proof valve 4 has a role of releasing the pressure to the outside when the pressure in the battery case 3 rises. In the case of a lithium ion battery, this explosion-proof valve 4 is generally designed to open at about 0.5 to 1.0 MPa.

The positive electrode plate 12 is a current collector in which a positive electrode mixture is held on both surfaces. For example, the current collector is an aluminum foil having a thickness of about 20 μm, and the paste-like positive electrode mixture is polyvinylidene fluoride as a binder to lithium cobalt oxide (LiCoO ₂ ), which is a lithium-containing oxide of a transition metal. And acetylene black as a conductive material are added and kneaded. The positive electrode plate 12 is obtained by applying this paste-like positive electrode mixture on both sides of the aluminum foil, followed by drying, rolling, and cutting into a strip.

  The negative electrode plate 14 is a current collector in which a negative electrode mixture is held on both surfaces. For example, the current collector is a copper foil having a thickness of 10 μm, and the paste-like negative electrode mixture is obtained by kneading after adding polyvinylidene fluoride as a binder to graphite powder. The negative electrode plate 14 is obtained by applying the paste-like negative electrode mixture on both sides of the copper foil, followed by drying, rolling, and cutting into strips.

  A porous film is used as the separator 15. For example, the separator 15 can be a polyethylene microporous film. The electrolyte solution impregnated in the separator is, for example, 1 mol / L of six fluorine in a mixed solution in which ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) are mixed at a ratio of 1: 1: 1. What added the lithium phosphoric acid phosphate can be used.

  A cartridge case (not shown) is provided adjacent to the explosion-proof valve 4 of such a nonaqueous electrolyte secondary battery E, and a gas ejection preventing material is accommodated in the cartridge case. Materials for the cartridge case include metal materials typified by SUS, Al, Al alloy, Mg alloy, Ti alloy, etc., highly corrosion resistant materials such as fluororesin, lightweight materials such as polypropylene and carbon fiber, and composite materials thereof. Is mentioned.

  The gas blowout prevention material is preferably filled with a space of, for example, about 10 to 50% by volume, rather than being fully filled in the cartridge case. If the filling rate is less than 50% by volume, there are too few gas ejection preventing materials, so that a sufficient gas ejection preventing effect may not be obtained. On the other hand, if the filling rate exceeds 90% by volume, the diffusibility of the ejection gas may be reduced. Since the contact efficiency with the gas ejection preventing material is lowered, the gas ejection preventing effect may be lowered.

  In the present embodiment, as the inorganic porous material constituting the gas ejection preventing material, a crystalline compound mainly composed of silicon dioxide and aluminum oxide and having a channel-type pore structure is particularly preferable. From the viewpoint of improving the absorption performance of low molecular weight gas components such as carbon monoxide and methane, those containing lithium are preferable.

  When this gas ejection preventing material does not contain lithium, the Si / Al ratio is preferably in the range of 2 to 5. When the Si / Al ratio is less than 2, the absorption rate of the ejected gas such as carbon monoxide and hydrocarbon gas is lowered. On the other hand, when the Si / Al ratio exceeds 5, the absorption rate of the low molecular weight hydrocarbon gas is lowered. Therefore, it is not preferable. The inorganic porous material may contain one or more elements or ions in addition to silicon dioxide and aluminum oxide.

  Moreover, when it contains lithium, it is preferable that the content rate of lithium is 1-20 mass%, and it is especially preferable that it is 2-5 mass%. If the lithium content is less than 1% by mass, the effect of improving the absorptivity of the low molecular weight gas component is not sufficient. In addition, the stability of the inorganic porous material may be impaired. In this case, the Si / Al ratio is preferably in the range of 1 to 2.4. When the Si / Al ratio is less than 1, the absorption rate of ejected gases such as carbon monoxide and methane is reduced. On the other hand, when the Si / Al ratio exceeds 2.4, the absorption rate of low molecular weight hydrocarbon gas is reduced. Therefore, it is not preferable.

  As such an inorganic porous material, zeolite is representative, and as this zeolite, any of A-type zeolite, X-type zeolite and β-type zeolite can be used. preferable. From the viewpoint of improving the absorption performance of low molecular weight gas components such as carbon monoxide and methane, zeolite containing lithium in the form of ions is preferable.

  The inorganic porous material preferably has a pore diameter of 3 to 10 mm, particularly preferably 5 to 9 mm. When the pore diameter is less than 3%, the absorption rate of the ejected gas such as carbon monoxide or hydrocarbon gas is lowered. On the other hand, when it exceeds 10%, the absorption rate of the low molecular weight hydrocarbon gas is lowered, which is not preferable.

Further, inorganic porous material has a specific surface area of preferably from 100~1000m ² / g. When the specific surface area of the inorganic porous material is less than 100 m ² / g, the contact area between the inorganic porous material and carbon monoxide, hydrocarbon gas or the like is small, and the absorption rate of the jet gas is small, while the specific surface area is 1000 m ^2. Even if exceeding / g, not only the improvement effect of the jet gas absorption rate is not obtained, but also the mechanical strength of the gas jet prevention material is lowered, which is not preferable.

  The inorganic porous material as described above preferably has an average particle diameter of 100 to 2000 μm, particularly 500 to 1500 μm. When the average particle diameter is less than 100 μm, the contact efficiency between the ejected gas and the inorganic porous material is deteriorated, and the effect of preventing the ejection is reduced. On the other hand, when the average particle diameter is more than 2000 μm, the ejected gas is between the particles. This is not preferable because it may pass through the air and the jetting prevention effect may be reduced.

  The gas ejection preventing material of the present embodiment may be molded using an appropriate method for the purpose of improving the substantial average particle diameter of the inorganic porous material as described above. Although there is no restriction | limiting in particular in the shape of a molded article, It is preferable to set it as shapes, such as a granule, a granule, a bead, a pellet, when the diffusibility of a jetty thing, filling property, and the ease of handling are considered.

  The gas ejection preventing material of the present embodiment using such an inorganic porous material has a gas absorption rate of 40% or more, particularly 50% or more, and particularly carbonization of ethane gas, ethylene gas, propane gas, propylene gas or the like. Excellent performance in absorbing hydrogen gas. In particular, when lithium is contained, it exhibits excellent performance in absorbing low molecular weight gas components such as carbon monoxide and methane.

  The gas ejection preventing material according to the present embodiment as described above is filled in a cartridge case having a detachable connection portion, and covers the explosion-proof valve 4 of the nonaqueous electrolyte secondary battery E directly or via piping. By connecting in this way, it can be set as a gas ejection prevention system. In this case, by forming the inflow portion and the outflow portion in the cartridge case and connecting the outflow portions of the plurality of cartridge cases, it is possible to improve the gas ejection prevention effect.

  And this gas ejection prevention system can be installed in electrical storages, such as a nonaqueous electrolyte secondary battery, and can be set as a secondary battery system. In this case, the liquid component and the gas component are separated between the battery explosion-proof valve and the gas ejection preventing material in the cartridge case for the purpose of avoiding the gas ejection preventing material in the cartridge case from coming into contact with the liquid component. It is preferable to provide gas-liquid separation means.

  The gas-liquid separation means is not particularly limited, but an electrolyte absorbing material is disposed between the battery explosion-proof valve and the gas ejection preventing material in the cartridge case for the purpose of preventing the liquefied electrolyte from vaporizing again. It is preferable for practical use.

  The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to the following examples.

(Test equipment)
As a test apparatus for evaluating a gas ejection preventing material for a secondary battery of the present invention, a simulation test apparatus for the behavior of electrolyte decomposition gas ejected from a lithium ion battery at a high temperature and a high pressure shown in FIG. 3 was manufactured.

  In FIG. 3, the gas ejection preventing material testing device 21 has a mixed gas heating storage container 22 and a sample (gas ejection preventing material) filling container 23, which are connected to a pipe line 26 via connecting members 24 and 25. It communicates with. An opening / closing valve 27 is provided in the middle of the pipe line 26, and an aluminum bag 28 for collection is further communicated with the outlet side of the sample filling container 23.

  The connecting member 24 is provided with a pressure gauge 29, and the connecting members 24 and 25 are provided with thermocouples 30 and 31. The mixed gas heating container 22, the connecting members 24 and 25, and the pipe line 26 can be heated by a mantle heater (not shown) as an overheating means, and the mantle heater and the thermocouples 30 and 31 are It is connected to a control device (not shown), and on / off control of the mantle heater can be performed according to the outputs of the thermocouples 30 and 31.

(Blank measurement test)
In the test apparatus 21 for the gas ejection preventing material as described above, the mixed gas heating container 22 is filled with a mixed gas having the composition shown in Table 1 so as to be 0.45 MPa at 20 ° C., and the sample filling container 23 is filled. Glass wool 10 mL was filled as a standard instead of the gas blowout prevention material.

  Subsequently, with the mantle heater in a state where the on-off valve 27 was closed, the mixed gas heating container 22, the connection members 24 and 25, and the inside of the pipe line 26 were heated to 300 ° C. or higher. When the pressure in the mixed gas heated storage container 22 reaches 0.93 MPa due to the expansion of the mixed gas, the on-off valve 27 is opened to supply the high temperature mixed gas to the sample filling container 23 via the conduit 26. did. The gas component that could not be absorbed in the sample filling container 23 was collected by an aluminum bag 28 provided at the outlet of the sample filling container 23. The amount of gas collected by the aluminum bag 28 at this time was 0.57L. Table 2 shows the results of analyzing the collected gas components.

Example 1
In the blank measurement test, the test was performed in the same manner except that the sample filling container 23 was filled with 10 mL (6.77 g) of X-type zeolite (cation: Ca type) having a pore diameter of 9 mm and Si / Al = 2.5. However, the gas collection amount of the aluminum bag 28 was 0.27L. Table 3 shows the absorption rate of the entire gas component at this time and the absorption rate of each gas component calculated from the analysis result of each gas component.

  In addition, the absorption rate of the whole gas component and the absorption rate of each gas component were computed based on the comparison with the gas collection amount of the aluminum bag 28 in a blank measurement test, and the result of a gas component analysis.

(Example 2)
In Example 1, when the sample filling container 23 was filled with 10 mL (6.44 g) of X-type zeolite (cation: Na type) having a pore diameter of 9 mm and Si / Al = 2.5, a test was performed in the same manner. The gas collection amount of the aluminum bag 28 was 0.13L. Table 3 shows the absorption rate of the gas components as a whole and the absorption rate of each gas component calculated from the analysis result of each gas component.

(Example 3)
In Example 1, a test was conducted in the same manner except that the sample filling container 23 was filled with 10 mL (6.86 g) of A-type zeolite having a pore diameter of 5 mm and Si / Al = 2. The amount was 0.16L. Table 3 shows the absorption rate of the gas components as a whole and the absorption rate of each gas component calculated from the analysis result of each gas component.

Example 4
In Example 1, a test was conducted in the same manner except that 10 mL (7.08 g) of A-type zeolite having a pore diameter of 4 mm and Si / Al = 2 was filled in the sample filling container 23. The amount was 0.23L. Table 3 shows the absorption rate of the gas components as a whole and the absorption rate of each gas component calculated from the analysis result of each gas component.

(Example 5)
In Example 1, a test was conducted in the same manner except that the sample filling container 23 was filled with 10 mL (7.14 g) of A-type zeolite having a pore diameter of 3 mm and Si / Al = 2. The amount was 0.34L. Table 3 shows the absorption rate of the gas components as a whole and the absorption rate of each gas component calculated from the analysis result of each gas component.

(Example 6)
In Example 1, a test was conducted in the same manner except that the sample filling container 23 was filled with 10 mL (7.57 g) of β-type zeolite having a pore diameter of 6 mm and Si / Al = 40. The amount was 0.34L. Table 3 shows the absorption rate of the gas components as a whole and the absorption rate of each gas component calculated from the analysis result of each gas component.

(Comparative Example 1)
In Example 1, when the test was done similarly except having filled the sample filling container 23 with 10 mL (3.24 g) of magnesium silicate, the amount of gas collected in the aluminum bag 28 was 0.52 g. Table 3 shows the absorption rate of the gas components as a whole and the absorption rate of each gas component calculated from the analysis result of each gas component.

  Table 4 shows the shapes, average particle diameters, tap densities, and specific surface areas of the gas ejection preventing materials of Examples 1 to 6 and Comparative Example 1.

  As is clear from Table 3, the gas ejection preventing materials of the secondary batteries of Examples 1 to 6 that did not contain lithium had a high absorption rate of carbon monoxide and hydrocarbon gas. Particularly in Examples 1 to 3 having a pore diameter of 5 mm or more and an Si / Al ratio of 2.5 or less, both the gas absorption rate and the absorption rate of each component were high.

(Example 7)
In Example 1, a test was conducted in the same manner except that the sample filling container 23 was filled with 10 mL (7.09 g) of lithium ion exchange type zeolite having a pore size of 5.6 mm and Si / Al = 2.12. The amount of gas collected by the bag 28 was 0.16L. Table 5 shows the absorption rate of the gas components as a whole and the absorption rates of the gas components calculated from the analysis results of the gas components.

(Example 8)
A test was conducted in the same manner as in Example 1 except that the sample filling vessel 23 was filled with 10 mL (6.71 g) of lithium ion exchange type zeolite having a pore size of 5.6 mm and Si / Al = 2.12. The amount of gas collected by the bag 28 was 0.14L. Table 5 shows the absorption rate of the gas components as a whole and the absorption rates of the gas components calculated from the analysis results of the gas components.

Example 9
In Example 1, a test was performed in the same manner except that the sample filling container 23 was filled with 10 mL (7.00 g) of lithium ion exchange type zeolite having a pore diameter of 6.1 mm and Si / Al = 2.5. The amount of gas collected by the bag 28 was 0.13L. Table 5 shows the absorption rate of the gas components as a whole and the absorption rates of the gas components calculated from the analysis results of the gas components.

(Example 10)
In Example 1, the test was performed in the same manner except that the sample filling container 23 was filled with 10 mL (7.17 g) of X-type zeolite (cation: Na type) having a pore size of 5.6 mm and Si / Al = 2.12. As a result, the amount of gas collected by the aluminum bag 28 was 0.13 L. Table 5 shows the absorption rate of the entire gas component and the absorption rate of each gas component calculated from the analysis result of each gas component.

  Table 6 shows the shape, average particle diameter, tap density, and specific surface area of the gas ejection preventing materials of Examples 7 to 10.

  As is clear from Table 5, the gas ejection preventing materials of the secondary batteries of Examples 7 to 9 containing lithium have a high absorption rate of carbon monoxide and hydrocarbon gas, and particularly compared with Example 10 not containing lithium. Thus, the absorption rate of low molecular weight gas components such as carbon monoxide and methane gas has been greatly improved. In particular, Examples 7 and 8 in which the Si / Al ratio was 2.12 were greatly improved in the absorptivity of the low molecular weight gas component compared to Example 9 in which the Si / Al ratio was 2.5.

  The gas ejection preventing material of the present invention as described above can prevent the ejection of flammable or toxic gas generated inside the secondary battery, so that consideration is given to safety and environmental problems of the secondary battery. As such, industrial applicability is extremely large.

1 ... Positive terminal (positive electrode)
2 ... Negative terminal (negative electrode)
3. Battery case (housing)
4 ... Explosion-proof valve 11 ... Positive electrode current collector (positive electrode)
13 ... Negative electrode current collector (negative electrode)
E ... Nonaqueous electrolyte type secondary battery (secondary battery)

Claims (11)

In order to absorb gas ejected when an abnormality occurs in a secondary battery comprising a case in which a positive electrode and a negative electrode are sealed together with an electrolyte, and an explosion-proof valve for releasing high-pressure gas inside the case when the internal pressure of the case rises Gas blowout prevention material for secondary batteries,
Ri Do inorganic porous material mainly composed of silicon dioxide and aluminum oxide,
A gas ejection preventing material for a secondary battery, wherein the inorganic porous material contains lithium .   2. The gas ejection preventing material according to claim 1, wherein the inorganic porous material has an elemental composition ratio in a range of Si / Al ratio of 2 to 5. 3.   The gas ejection preventing material according to claim 1 or 2, wherein the inorganic porous material is A-type or X-type zeolite. 2. The gas ejection preventing material for a secondary battery according to claim 1 , wherein the inorganic porous material has a lithium content of 1 to 20 mass%. The gas ejection preventing material according to any one of claims 1 to 4, wherein the inorganic porous material has an elemental composition ratio in a range of Si / Al ratio of 1 to 2.4. The gas ejection preventing material according to any one of claims 1 to 5 , wherein the inorganic porous material has a pore diameter of 3 to 10 mm. The inorganic porous material, the gas blowout preventer material according to any one of claims 1 to 6, the specific surface area is characterized by a 100~1000m ² / g. The gas ejection preventing material according to any one of claims 1 to 7 , wherein the inorganic porous material in the previous period has an average particle diameter of 100 to 2000 µm. The gas ejection preventing material according to any one of claims 1 to 8 , wherein the inorganic porous material is a molded product of powder. A gas ejection preventing system using the gas ejection preventing material according to any one of claims 1 to 9 . A secondary battery system comprising the gas ejection prevention system according to claim 10 .

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