JP2009224141A - Slurry-using secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a slurry-using secondary battery wherein unevenness of battery reaction is not easily caused and structural deterioration of electrodes is not caused, while making the best use of advantages of a lithium secondary battery. <P>SOLUTION: This slurry utilization type secondary battery 10 is equipped with a separator 18 to divide the inside of a case 12 into a positive electrode chamber 14 and a negative electrode chamber 16, a positive electrode current-collecting plate 20 disposed in the positive electrode chamber 14, and a negative electrode current-collecting plate 22 disposed in the negative electrode chamber 16. A positive electrode side circulation passage 26 in which a pump 28 is assembled is provided between the positive electrode chamber 14 and a positive electrode slurry tank 24 to store positive electrode slurry, and a negative electrode side circulation passage 32 in which a pump 34 is assembled is provided between the negative electrode chamber 16 and a negative electrode slurry tank 30 to store negative electrode slurry. In this slurry utilization type secondary battery 10, high discharge capacity is obtained as a result of performing charge and discharge by setting a charge and discharge current at 16 mA with the pumps 28, 34 driven. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a slurry-based secondary battery in which a positive electrode slurry and a negative electrode slurry are accommodated in a positive electrode chamber and a negative electrode chamber, respectively.

2. Description of the Related Art Conventionally, redox flow batteries that perform charging / discharging by circulating an electrolytic solution containing a battery active material are known. For example, in the redox flow battery of Patent Document 1, an electrolyte containing vanadium as an active material is used for both positive and negative electrodes, and each electrolyte is charged and discharged while being sent and circulated from a tank to a cell by a pump.
JP2007-188729

  However, since the redox flow battery uses an aqueous electrolyte such as dilute sulfuric acid aqueous solution, there are problems that the battery voltage is as low as about 1.3 to 1.5 V and the energy density is low.

  On the other hand, in lithium secondary batteries (including lithium ion secondary batteries and metallic lithium secondary batteries) that use a non-aqueous electrolyte as the electrolyte, charging and discharging are performed by exchanging lithium ions between the positive electrode and the negative electrode. Is called. Such a lithium secondary battery has an advantage that a high battery voltage exceeding the electrolysis voltage of water can be obtained and the energy density is also high.

  However, when a non-uniform reaction occurs inside the electrode, there is a problem that unevenness of the battery reaction accumulates and the energy of the battery cannot be fully utilized. That is, when performing slow charging / discharging, a substantially uniform reaction occurs inside the electrode, but when performing rapid charging / discharging, a non-uniform reaction occurs inside the electrode, and there are locally high temperature spots. Arise. Since the reaction is likely to proceed at such a high temperature place, a vicious cycle in which the temperature becomes higher is caused, and the energy of the battery may not be fully utilized. In addition, lithium ions are inserted into and desorbed from the active material, resulting in a change in the volume of the active material. Due to the change in volume, the electrode structure deteriorates during a long charge / discharge cycle, resulting in a short battery life. There was also a problem of becoming.

  The present invention has been made to solve such problems, and provides a slurry-based secondary battery that takes advantage of a lithium secondary battery and does not cause unevenness of battery reaction and does not cause structural deterioration of an electrode. The main purpose is to do.

  In order to achieve the above-described object, the present inventors have prepared a positive electrode slurry in which lithium nickelate as a positive electrode active material and carbon black as a conductive material are dispersed in a non-aqueous electrolyte, and an artificial material as a negative electrode active material. When a secondary battery was assembled using a negative electrode slurry in which graphite and carbon black as a conductive material were dispersed in a non-aqueous electrolyte, it was found that charge and discharge were possible, and the present invention was completed. .

That is, the slurry-based secondary battery of the present invention is
A lithium ion conductive solid electrolyte membrane that separates the inside of the case into a positive electrode chamber and a negative electrode chamber;
A positive electrode slurry in which a positive electrode active material accommodated in the positive electrode chamber and capable of occluding and releasing lithium ions is dispersed in a non-aqueous electrolyte having ion conductivity;
A positive electrode current collector disposed in the positive electrode chamber and capable of transferring electrons to and from the positive electrode active material;
A negative electrode slurry in which a negative electrode active material accommodated in the negative electrode chamber and capable of occluding and releasing lithium ions is dispersed in a non-aqueous electrolyte having ion conductivity;
A negative electrode current collector disposed in the negative electrode chamber and capable of transferring electrons to and from the negative electrode active material;
It is equipped with.

  In this slurry-based secondary battery, a high battery voltage exceeding the electrolysis voltage of water is obtained, and the advantage of the lithium secondary battery that the energy density is high is obtained. In addition, since the slurry is used for both the positive and negative electrodes, even if high and low temperatures occur in the slurry, the local temperature rise is mitigated by the flow of the slurry, resulting in uneven battery reaction. Hateful. Furthermore, even if a volume change occurs due to insertion / extraction of lithium ions, since the slurry is used for both the positive and negative electrodes, there is no possibility of cracking compared to the case of a solid, so that the structure of the electrode is not deteriorated. From the above, according to the slurry-based secondary battery of the present invention, it is possible to obtain the effect that the unevenness of the battery reaction hardly occurs and the structure of the electrode does not deteriorate while taking advantage of the lithium secondary battery.

  The slurry-based secondary battery of the present invention includes a positive electrode side circulation path provided in the positive electrode chamber, a positive electrode side circulation pump that circulates the positive electrode slurry accommodated in the positive electrode chamber through the positive electrode side circulation path, You may provide the negative electrode side circulation path provided in the negative electrode chamber, and the negative electrode side circulation pump which circulates the said negative electrode slurry accommodated in the said negative electrode chamber through the said negative electrode side circulation path. In this case, the battery reaction is promoted by circulating the positive and negative electrode slurry, so that the discharge capacity per active material is increased and the unevenness of the battery reaction is further less likely to occur. The slurry-based secondary battery is further provided in the middle of the positive electrode side circulation path, and is provided in the middle of the positive electrode slurry tank and the negative electrode side circulation path, and stores the negative electrode slurry. A negative electrode slurry tank. In this case, the active material in the positive and negative electrode slurry tanks is involved in the battery reaction, and thus the discharge capacity can be easily increased. In addition, when the installation location of the case is small, the amount of the active material involved in the battery reaction can be reduced by reducing the size of the case and installing a large positive / negative slurry tank away from the installation location of the case. Since it can be ensured, a large discharge capacity can be obtained.

  In the slurry-based secondary battery of the present invention, the positive electrode slurry and the negative electrode slurry may have electrical conductivity. In this way, the positive electrode current collector can exchange electrons with the positive electrode active material via the positive electrode slurry, and the negative electrode current collector can exchange electrons with the negative electrode active material via the negative electrode slurry. In order to make the positive and negative slurry have electrical conductivity, for example, a conductive material may be included in each slurry.

  In the slurry-based secondary battery of the present invention, the positive electrode current collector and the negative electrode current collector may have holes through which the positive electrode slurry and the negative electrode slurry can pass, respectively. In this way, when the positive electrode slurry passes through the holes provided in the positive electrode current collector, electrons can be transferred between the positive electrode active material and the positive electrode current collector, and the negative electrode slurry is provided in the negative electrode current collector. Electrons can be exchanged between the negative electrode active material and the negative electrode current collector when moving between the holes. At this time, it is preferable that the positive electrode current collector and the negative electrode current collector are disposed in the vicinity of the lithium ion conductive solid electrolyte membrane or are in close contact with the lithium ion conductive solid electrolyte membrane. In this way, the exchange of electrons between the positive electrode active material and the positive electrode current collector or between the negative electrode active material and the negative electrode current collector and the transfer of lithium ions between the positive electrode chamber and the negative electrode chamber can be performed. Since the reaction is performed in the vicinity, the resistance of the exchange reaction between electrons and ions is reduced, and the discharge capacity is increased. It goes without saying that the positive and negative electrode slurry may have electrical conductivity and the positive and negative electrode current collectors may be provided with holes.

  In the slurry-based secondary battery of the present invention, the lithium ion conductive solid electrolyte membrane is not particularly limited as long as it is a composition that can withstand the use conditions of the secondary battery. For example, lithium ion conductive glass (oxide) Glass and sulfide glass).

In the slurry-based secondary battery of the present invention, the positive electrode slurry is a dispersion liquid in which a positive electrode active material capable of occluding and releasing lithium ions is dispersed in a non-aqueous electrolyte having ion conductivity. The positive electrode active material is not particularly limited as long as it is a material that releases lithium ions during charge and occludes lithium ions during discharge, but has a layered structure such as lithium cobaltate (LiCoO ₂ ) or lithium nickelate (LiNiO ₂ ). Examples thereof include lithium composite oxides, spinel structure lithium composite oxides such as lithium manganate (LiMn ₂ O ₄ ), and olivine structure lithium composite oxides such as lithium iron phosphate (LiFePO ₄ ). The non-aqueous electrolyte solution is not particularly limited as long as it has ion conductivity, and examples thereof include an organic solvent in which a lithium salt is dissolved. As the lithium salt, for example, LiPF ₆ , LiClO ₄ , LiBF ₄ , Li (CF ₃ SO ₂ ) ₂ N, or the like can be used. As an organic solvent, for example, ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (γ-BL), diethyl carbonate (DEC), dimethyl carbonate (DMC) and the like are used for conventional secondary batteries and capacitors. An organic solvent is mentioned. These may be used alone or in combination.

In the slurry-based secondary battery of the present invention, the positive electrode current collector is not particularly limited, but an electrochemically stable material is used in the potential range when the positive electrode active material used is charged and discharged. It is preferable. Examples of such a positive electrode current collector include a metal plate such as stainless steel, aluminum, and copper, and a metal mesh. Also, transparent conductive materials such as InSnO ₂ , SnO ₂ , ZnO, In ₂ O ₂ , fluorine-doped tin oxide (SnO ₂ : F), antimony-doped tin oxide (SnO ₂ : Sb), tin-doped indium oxide (In ₂ O ₃ : Sn), ZnO, Al-doped zinc oxide (ZnO: Al), Ga-doped zinc oxide (ZnO: Ga) and other materials doped with a single layer or laminated layer such as glass or polymer You may use what was formed in.

  Such a positive electrode current collector needs to be able to exchange electrons with the positive electrode active material. For this purpose, a conductive material may be dispersed in the positive electrode slurry. Examples of the conductive material include carbon blacks such as ketjen black, acetylene black, channel black, furnace black, lamp black, and thermal black, natural graphite such as flake graphite, artificial graphite, expanded graphite, and the like. It may be graphites, conductive fibers such as carbon fibers and metal fibers, metal powders such as copper, silver, nickel, and aluminum, or organic conductive materials such as polyphenylene derivatives. These may be used alone or in combination. Alternatively, a hole through which the positive electrode slurry can pass is provided in the positive electrode current collector, and electrons may be exchanged between the positive electrode current collector and the positive electrode slurry through the hole.

  In the slurry-based secondary battery of the present invention, the negative electrode slurry is a dispersion liquid in which a negative electrode active material capable of occluding and releasing lithium ions is dispersed in a nonaqueous electrolytic solution having ion conductivity. The negative electrode active material is not particularly limited as long as it is a material that occludes lithium ions at the time of charging and releases lithium ions at the time of discharging. For example, in addition to metallic lithium and lithium alloy, a carbonaceous material that occludes and releases lithium ions can be mentioned. It is done. Examples of the lithium alloy include an alloy of lithium with aluminum, tin, magnesium, indium, calcium, and the like. Examples of the carbonaceous material that absorbs and releases lithium ions include natural graphite, artificial graphite, coke, mesophase pitch-based carbon fiber, spherical carbon, and resin-fired carbon. In addition, the electrolyte and solvent which comprise a non-aqueous electrolyte solution may be the same, and may differ in a positive electrode slurry and a negative electrode slurry.

  In the slurry-based secondary battery of the present invention, it is preferable to use a material that is electrochemically stable in the potential range when the negative electrode active material to be used is charged and discharged as the negative electrode current collector. As such a negative electrode current collector, the same material as the above-described positive electrode current collector can be used, and thus the description thereof is omitted here. In addition, the negative electrode current collector needs to be able to exchange electrons with the negative electrode active material. For this purpose, a conductive material may be dispersed in the negative electrode slurry, or the negative electrode current collector may have a negative electrode slurry. May be provided, and electrons may be exchanged with the negative electrode slurry through the hole. In addition, about the electrically conductive material, since the thing similar to what was mentioned above can be used, the description is abbreviate | omitted here. Further, when a carbonaceous material is used as the negative electrode current collector, the carbonaceous material may also be used as a conductive material.

[Example 1]
The positive electrode slurry was prepared as follows. That is, commercially available lithium nickelate (LiNi _0.8 Co _0.15 Al _0.05 O ₂ : average particle size 3 μm) as the positive electrode active material, carbon black (average particle size 20 nm) as the positive electrode conductive material, and 1M LiPF as the positive electrode electrolyte. ₆ in 30% EC + 70% DEC was used. This positive electrode active material / conductive material / electrolytic solution was mixed at a ratio of 20/5/75 wt% in an Ar gas glove box to obtain a positive electrode slurry. The positive electrode slurry had a volume resistivity of 10 ³ Ωcm in the case of direct current and 10 ² Ωcm in the case of alternating current of 1 kHz, and electrical conductivity and ionic conductivity were confirmed.

The negative electrode slurry was prepared as follows. That is, commercially available artificial graphite (average particle size 1 μm) was used as the negative electrode active material, carbon black (average particle size 20 nm) was used as the negative electrode conductive material, and 1M LiPF ₆ in 30% EC + 70% DEC was used as the negative electrode electrolyte. This negative electrode active material / conductive material / electrolytic solution was mixed to 20/5/75 wt% in an Ar gas glove box to obtain a negative electrode slurry. The volume resistivity of the negative electrode slurry was 10 ³ Ωcm in the case of direct current and 10 ² Ωcm in the case of alternating current of 1 kHz, and electrical conductivity and ionic conductivity were confirmed. In addition, since the commercially available artificial graphite used here has a large particle size and a small amount of addition, it hardly contributes to the electrical conductivity of the slurry.

Next, a slurry-based secondary battery 10 having a schematic configuration shown in FIG. 1 was assembled. The slurry-based secondary battery 10 includes a case 12, a separator 18 that separates the inside of the case 12 into a positive electrode chamber 14 and a negative electrode chamber 16, a positive current collector 20 disposed in the positive electrode chamber 14, a negative electrode chamber 16 and a negative electrode current collector plate 22 disposed on the same. Each of the slurry tanks 14 and 16 has a length and width of 4 cm × 4 cm, the separator 18 has a length and width of 4 cm × 4 cm and a thickness of 0.5 mm, and each of the current collecting plates 20 and 22 has a length and width of 4 cm × 4 cm and a thickness of 0.1 mm. And the current collecting plates 20 and 22 were 2.5 mm, and the volumes of the slurry tanks 14 and 16 were 4 cm ³ . As the separator 18, a lithium ion conductive glass ceramic LIC-GC thin plate manufactured by OHARA was used. This has the characteristics of an ionic conductivity at 25 ° C. of 1.0 × 10 ⁻⁴ Scm ⁻¹ and a bending strength of 140 N / mm ² . The material of the case 12 is not particularly limited as long as it has no electrical conductivity and has resistance to organic solvents, and examples thereof include polypropylene (PP), polyethylene (PE), polytetrafluoroethylene (PTFE), and ceramics. .

Further, a positive electrode side circulation path 26 is provided between the positive electrode chamber 14 and the positive electrode slurry tank 24 for storing the positive electrode slurry, and a positive electrode side circulation pump 28 is attached in the middle of the positive electrode side circulation path 26. On the other hand, a negative electrode side circulation path 32 was provided between the negative electrode chamber 16 and the negative electrode slurry tank 30 for storing the negative electrode slurry, and a negative electrode side circulation pump 34 was attached in the middle of the negative electrode side circulation path 32. The positive electrode side circulation system (that is, the positive electrode chamber 14, the positive electrode slurry tank 24, and the positive electrode side circulation path 26) is filled with 12.5 cm ³ of the positive electrode slurry, and the negative electrode side circulation system (that is, the negative electrode chamber 16 and the negative electrode slurry tank). 30 and the negative electrode side circulation path 32) were filled with 15 cm ³ of negative electrode slurry. The positive electrode active material in the positive electrode slurry in the circulation system is 3.62 g, and the negative electrode active material in the negative electrode slurry in the circulation system is 2.70 g. In the slurry-based secondary battery 10, each slurry was filled in an Ar gas glove box, the battery was sealed, taken out into the atmosphere, and the following charge / discharge test was performed.

The charge / discharge test was conducted as follows. That is, the flow rate of the positive side circulation pump 28 is set to 6.25 cm ³ / min, the flow rate of the negative side circulation pump 34 is set to 7.5 cm ³ / min, CC 4.1V is charged at a current of 16 mA (constant current) and a temperature of 25 ° C. The charge / discharge test of /CC3.0V discharge was done and the change of the charge / discharge capacity was measured. The results are shown in Table 1.

[Example 2]
A charge / discharge test was conducted in the same manner as in Example 1 except that the positive and negative circulation pumps 28 and 34 were stopped in Example 1. The results are shown in Table 1.

[Example 3]
2 except that the slurry-based secondary battery 50 in which the positive and negative current collectors 60 and 62 shown in FIG. 2 are arranged in close contact with the separator 18 instead of the positive and negative current collectors 20 and 22 in Example 1. Were the same as in Example 1 were subjected to a charge and discharge test. The results are shown in Table 1. The positive electrode and negative electrode current collector plates 60 and 62 are provided so that the holes 60a and 62a each having a diameter of 0.5 mm have an opening ratio of 60%. The positive electrode slurry can pass through the holes 60 a of the positive electrode current collector plate 60, and the negative electrode slurry can pass through the holes 62 a of the negative electrode current collector plate 62.

[Example 4]
A charge / discharge test was conducted in the same manner as in Example 3 except that the conductive material was not added to the positive electrode slurry and the negative electrode slurry in Example 3. The results are shown in Table 1. The volume resistivity of each slurry was ∞Ωcm in the case of direct current and 3 × 10 ² Ωcm in the case of alternating current of 1 kHz, and it was confirmed that there was almost no electrical conductivity although there was ionic conductivity.

[Comparative Example 1]
A charge / discharge test was conducted in the same manner as in Example 1 except that the conductive material was not added to the positive electrode slurry and the negative electrode slurry in Example 1. The results are shown in Table 1.

[Evaluation of charge / discharge test]
As is clear from Table 1, in Comparative Example 1, almost no charge / discharge was performed, but in Examples 1 to 4, charge / discharge was possible. The reason why charging / discharging was not possible in Comparative Example 1 was that each slurry had ionic conductivity, but no electrical conductivity, so that electrons could not be transferred between each current collector and each active material. It is thought to be caused by.

  In Example 1, a discharge capacity of 141 mAh / g was obtained per positive electrode active material in the circulation system. Therefore, although the charge / discharge reaction (battery reaction) occurs only in the case 12, the active materials in the circulation paths 26 and 32 and the slurry tanks 24 and 30 are involved in the charge / discharge reaction by circulating each slurry. I understand.

  In Example 2, a discharge capacity of 39 mAh / g per positive electrode active material in the circulation system was obtained. Since this is a state in which no circulation occurs, a discharge capacity of 121 mAh / g is obtained when converted to the positive electrode active material in the case 12. Thus, it can be seen that when the circulation is stopped, only the active material in the case 12 is involved in charging and discharging. Moreover, when not circulating, since the discharge capacity per positive electrode active material involved in the charge / discharge reaction is reduced, it can be said that the charge / discharge reaction is promoted by circulation.

  In Example 3, a discharge capacity of 158 mAh / g per positive electrode active material in the circulation system was obtained. This is presumably because the resistance of the exchange reaction between electrons and ions that occurs during the charge / discharge reaction is reduced by bringing the current collector plates 60 and 62 with holes 60a and 62a into close contact with the separator 18. According to this discharge capacity, considering the irreversible capacity of the potential window, the negative electrode active material, and the positive electrode active material, it can be said that almost 100% of the charge / discharge reaction was performed.

  In Example 4, a discharge capacity of 102 mAh / g per positive electrode active material in the circulation system was obtained. The reason for charging / discharging is considered as follows although there is almost no electric conductivity in each slurry. That is, the holes 60a and 62a are formed in the current collector plates 60 and 62 and brought into close contact with the separator 18, thereby reducing the resistance of the exchange reaction between electrons and ions that occurs during the charge / discharge reaction. It is considered that the positive electrode active material in contact with both of the plates 60 and the negative electrode active material in contact with both of the separators 18 and the negative electrode current collector plate 62 efficiently caused a charge / discharge reaction. Also, by circulation, many positive electrode active materials flow while contacting both the separator 18 and the positive electrode current collector plate 60, and many negative electrode active materials flow while contacting both the separator 18 and the negative electrode current collector plate 62. Doing this is also considered to be a factor.

  From these results, it was found that charging and discharging were possible with the slurry-based secondary batteries 10 and 50 of Examples 1 to 4. In order to enable charging and discharging, it can be said that it is necessary to be able to exchange electrons between the positive electrode current collector plate 20 and the positive electrode slurry or between the negative electrode current collector plate 22 and the negative electrode slurry. . Such transfer of electrons may be realized by adding a conductive material to each slurry to impart electrical conductivity (Examples 1 and 2), or both current collecting plates 60 provided with holes 60a and 62a. 62 may be realized by closely contacting the separator 18 (Example 4), or may be realized by both of them (Example 3). Furthermore, it was also found that by circulating each slurry, all the active materials in the circulation system can be involved in the charge / discharge reaction and the charge / discharge reaction can be promoted.

  As described above in detail, according to the slurry-based secondary batteries 10 and 50, a high battery voltage exceeding the electrolysis voltage of water can be obtained, and the advantage of the lithium secondary battery that the energy density is also high can be obtained. In addition, since both the positive and negative electrodes use slurry, even if high temperature and low temperature are generated in the slurry, heat is more easily diffused than in the case of a solid, so that unevenness in battery reaction is less likely to occur. Furthermore, even if a volume change occurs due to insertion / extraction of lithium ions, since the slurry is used for both the positive and negative electrodes, there is no possibility of cracking compared to the case of a solid, so that the structure of the electrode is not deteriorated.

  In the slurry-based secondary batteries 10 and 50 described above, the positive electrode slurry can be replaced with a new one when the positive electrode slurry is deteriorated, or the negative electrode slurry can be replaced with a new one when the negative electrode slurry is deteriorated. In this way, since only the deteriorated part can be exchanged at the time of deterioration, recycling becomes easy.

  In the slurry-based secondary batteries 10 and 50 described above, the shape of the positive electrode slurry tank 24 and the negative electrode slurry tank 30 may be arbitrary, so that even if there is a restriction on the installation location, the shape is determined according to the installation location. Can be applied. For example, in a mobile body such as a hybrid vehicle or an electric vehicle, it is necessary to install a secondary battery in a limited space, and there are great restrictions on the installation location. However, slurry-based secondary batteries 10 and 50 are used as power sources for such a mobile body. Can also be adopted.

  In the slurry-based secondary batteries 10 and 50 described above, it is necessary to drive the positive electrode side circulation pump 28 and the negative electrode side circulation pump 34, but when mounted on a vehicle, rotation of a crankshaft, a propeller shaft, or the like as a drive source. Shaft rotation may be used.

  In the slurry-based secondary batteries 10 and 50 described above, a heat radiating portion may be provided in at least one of the positive electrode side circulation path 26 and the negative electrode side circulation path 32. In this way, it is possible to effectively prevent the temperature of the secondary battery from becoming high due to the battery reaction. At this time, a device that requires warm-up or warming (for example, an engine or a water heater immediately after startup) may be used as the heat radiating unit. In this way, effective use of exhaust heat becomes possible. Alternatively, a heat receiving part may be provided in at least one of the positive electrode side circulation path 26 and the negative electrode side circulation path 32. In this case, heat is received within a range that does not hinder the use of the secondary battery. In this way, by receiving the heat of a device that requires cooling (for example, an engine, a motor, an electric circuit, a harness, etc. during high-load operation) at the heat receiving portion, the device can be maintained at an appropriate temperature.

  In the slurry-based secondary batteries 10 and 50 described above, the case 12 may have elasticity or flexibility. In this way, even if the positive and negative electrode slurry expands in volume due to insertion and extraction of lithium ions, the expansion can be absorbed by the elasticity or flexibility of the case. Instead of or in addition to the case 12, the tanks 24 and 30 may be elastic or flexible, and the circulation paths 26 and 32 may be formed of elastic or flexible tubes. Good.

  In the slurry-based secondary batteries 10 and 50 described above, the tanks 24 and 30 may be omitted and the pumps 28 and 34 may be driven so that the slurry circulates in the circulation paths 26 and 32. Alternatively, the tanks 24 and 30, the pumps 28 and 34, and the circulation paths 26 and 32 may be omitted so that the slurry is not circulated.

2 is an explanatory diagram showing a schematic configuration of a slurry-based secondary battery 10 of Example 1. FIG. 6 is an explanatory diagram showing a schematic configuration of a slurry-based secondary battery 50 of Example 3. FIG.

Explanation of symbols

10, 50 Slurry type secondary battery, 12 case, 14 positive electrode chamber, 16 negative electrode chamber, 18 separator, 20, 60 positive electrode current collector plate, 22, 62 negative electrode current collector plate, 24 positive electrode slurry tank, 26 positive electrode side circulation path , 28 Positive electrode side circulation pump, 30 Negative electrode slurry tank, 32 Negative electrode side circulation path, 34 Negative electrode side circulation pump, 60a, 62a hole.

Claims (6)

A lithium ion conductive solid electrolyte membrane that separates the inside of the case into a positive electrode chamber and a negative electrode chamber;
A positive electrode slurry in which a positive electrode active material accommodated in the positive electrode chamber and capable of occluding and releasing lithium ions is dispersed in a non-aqueous electrolyte having ion conductivity;
A positive electrode current collector disposed in the positive electrode chamber and capable of transferring electrons to and from the positive electrode active material;
A negative electrode slurry in which a negative electrode active material accommodated in the negative electrode chamber and capable of occluding and releasing lithium ions is dispersed in a non-aqueous electrolyte having ion conductivity;
A negative electrode current collector disposed in the negative electrode chamber and capable of transferring electrons to and from the negative electrode active material;
A slurry-based secondary battery comprising: The slurry-based secondary battery according to claim 1,
A positive electrode side circulation path provided in the positive electrode chamber;
A positive electrode side circulation pump for circulating the positive electrode slurry accommodated in the positive electrode chamber through the positive electrode side circulation path;
A negative electrode side circulation path provided in the negative electrode chamber;
A negative electrode side circulation pump for circulating the negative electrode slurry accommodated in the negative electrode chamber through the negative electrode side circulation path;
A slurry-based secondary battery comprising: The slurry-based secondary battery according to claim 2,
A positive electrode slurry tank provided in the middle of the positive electrode side circulation path for storing the positive electrode slurry;
A negative electrode slurry tank that is provided in the middle of the negative electrode side circulation path and stores the negative electrode slurry;
A slurry-based secondary battery comprising: The positive electrode slurry and the negative electrode slurry have electrical conductivity.
The slurry utilization secondary battery of any one of Claims 1-3. The positive electrode current collector and the negative electrode current collector have holes through which the positive electrode slurry and the negative electrode slurry can pass, respectively.
The slurry utilization secondary battery of any one of Claims 1-4. The positive electrode current collector and the negative electrode current collector are disposed in the vicinity of the lithium ion conductive solid electrolyte membrane or are in close contact with the lithium ion conductive solid electrolyte membrane,
The slurry-based secondary battery according to claim 5.

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