JP5971705B2 - Continuous production equipment for organic sulfur positive electrode materials for secondary batteries - Google Patents

Description

  The present invention relates to an apparatus for continuously producing an organic sulfur-based active material that is mainly useful as a positive electrode active material for lithium ion or sodium ion secondary batteries.

Lithium ion secondary batteries are widely used as power sources for portable electronic devices because of their small size and high energy density. As the positive electrode active material, a layered compound such as LiCoO ₂ is mainly used (for example, see Patent Document 1). However, when these compounds are fully charged and exposed to a high temperature, oxygen tends to be desorbed, which tends to cause an oxidative exothermic reaction of the non-aqueous electrolyte. In recent years, demand for electric vehicle applications has increased, and there has been a demand for positive electrode materials that are safer, have a wider required operating temperature range (-30 ° C to 60 ° C), and have a large capacity, output, and durability. Yes.
Examples of such positive electrode active materials include Fe, Mn, Ni in addition to Co, oxide-based positive electrodes to which various additives are added, and olivine phosphate compounds LiMPO ₄ (LiMnPO ₄ , LiFePO ₄ , LiCoPO _4, etc.). Proposed. However, none of these exemplified materials shows a stable capacity of 250 mAh / g or more, and a battery having a usable temperature range required for automobiles, etc., safety and large capacity, and large output characteristics. No material has ever existed.

On the other hand, sulfur has attracted attention as a positive electrode active material that is inexpensive, has a large amount of resources, has a low environmental load, has a high theoretical charge / discharge capacity of lithium ions, and does not release oxygen at high temperatures. However, sulfur alone has a high electric resistance, and when it was operated as an electrode by adding a conductive auxiliary agent, elution into the electrolytic solution was remarkable and the cycle characteristics were poor.
In recent years, it has been found that a composite obtained by heating this sulfur with an organic substance exhibits high capacity, good cycle characteristics, and rate characteristics.
The present applicants manufactured a battery incorporating these organic sulfur-based positive electrode materials, and this battery has a usable temperature range as a secondary battery used in automobiles, safety and large capacity, and large output characteristics. It is confirmed that it is a real battery.

In Non-Patent Document 1, Wang et al. Of the Chinese Academy of Sciences synthesized a cathode material capable of taking in and out Li by reacting polyacrylonitrile (hereinafter referred to as PAN) with sulfur at 300 ° C., 13C NMR, FTIR, XPS, etc. It is described that characterization was performed. In this document, sulfur is described as being combined with an organic substance.
In Non-Patent Document 2, C. Lai et al. Of Nankai University in China created activated carbon with a surface area of 1473 m ² / g by heat-treating PAN with sodium carbonate in an Ar atmosphere at 750 ° C., and mixing it with sulfur. An organic sulfur composite containing 57% sulfur is produced by heat treatment at ℃, and this material has a capacity of 1155 mAh / g as a cathode material for lithium-ion batteries and has a capacity of 745 mAh / g even after 84 cycles Is described.
In Non-Patent Document 3, B. Zhang et al. Of Nankai University in China made a composite in which a sulfur acetylene black mixture was heated up to 300 ° C for 6 hours at 149 ° C and mixed with a ball mill and SEM, XRD, fine It is described that comparison was made by pore size distribution, CV, impedance method, and that the heat-treated composite showed a capacity of 500 mAh / g after 50 cycles, but the one that was not heat-treated remained at a low capacity. .
Non-Patent Document 4 describes the result of Shahab et al. Of Iraqi Mosul University examining the amount of sulfur at various temperatures for an organic sulfur composite obtained by reacting bitumen and sulfur at 400 ° C.
Non-Patent Document 5 states that Sun et al. Of Beijing Chemical University improve charge / discharge characteristics and cycle characteristics by using gelatin instead of conventional PEO as a sulfur binder, which is a positive electrode material for lithium-sulfur secondary batteries. And that gelatin does not swell in the organic solvent of the electrolyte, and that the effect of suppressing grain graining by SEM observation after the cycle test has been found.
In Non-Patent Document 6, Trofimov of the Siberian branch of the Russian Academy of Sciences reviews polymer sulfuration and charge / discharge. The structures of compounds produced by sulfuration of various polymers including polyethylene are shown, and the number of radicals and CV by ESR are reported.
In Non-Patent Document 7, Wei et al. Of Shanghai Jiao Tong University used 92 wt.% Acrylonitrile-8 wt.% Methyl acrylate polymer fiber (inexpensive commercial product) instead of conventional PAN, and used MWCNT (multi-wall) Carbon nanotubes) were added as conductive aids, 1 g of fiber, 0.1 g of MWCNT, 10 g of sulfur were ball milled in ethanol, and a composite containing 35 wt% sulfur heat-treated in nitrogen at 300 ° C. for 4 hours, and It is described that this composite exhibited a capacity of 560 mAh / g, 96.5% after 0.5C100 cycle, and 387 mAh / g at 7C.

As described above, many studies on organic sulfur-based positive electrode materials have been reported in recent years.
As can be seen from this, the organic sulfur-based positive electrode material is inexpensive, has abundant resources, is composed of harmless sulfur and organic matter, has low environmental impact, has high lithium ion charge / discharge capacity, and Since it is a material that is stable at high temperatures and does not release oxygen, it is very promising as a positive electrode material for sodium ion secondary batteries as well as a positive electrode material for next-generation lithium ion secondary batteries.

  While organic sulfur-based positive electrode materials are such attractive materials, there are various difficulties in their synthesis and production. Specifically, unlike the synthesis of oxide-based positive electrode materials that have been performed exclusively by the firing method, hydrothermal synthesis method, etc., a sulfurization reaction step is required in which an organic substance and sulfur are reacted by heating. . Furthermore, in order to give a sufficient capacity to the product by the inventors' many years of study, the treatment is performed in a state where a sufficient amount of sulfur is present in the organic matter at a temperature of 350 ° C. to 400 ° C. where sulfur is easily evaporated. I found it necessary to do. During this treatment process, highly toxic hydrogen sulfide is generated by the extraction of hydrogen from organic substances by sulfur. Since hydrogen sulfide is a dangerous gas that can be killed instantly if a gas with a concentration of 0.1% is inhaled, strict management is required.

  In addition, sulfur is also deposited on the flow of the generated hydrogen sulfide and is cooled at the outlet in an attempt to get out of the heating vessel, and the precipitated sulfur may cause clogging of the gas outlet of the heating vessel. In this case, pressurized hydrogen sulfide accumulates in the heating container. However, the hydrogen sulfide that has been pressurized and stored is difficult to safely process during the opening of the container, and is accidentally ejected all at once. It was very dangerous because it might leak.

  In addition, the organic sulfur-based positive electrode material synthesized in the heating container contains unreacted sulfur that dissolves in the electrolyte inside the battery and reduces the life of the battery. Treatment is required, and hydrogen sulfide may be generated during sulfur removal. Thus, it is difficult to obtain an organic sulfur-based positive electrode material in both synthesis and purification, so a series of these synthesis and purification operations can be performed quickly and in large quantities in a safe and environmentally friendly manner. However, there has been no such device in the past.

JP 2009-252630 A

J. Wang, J. Yang, C. Wan, K. Du, J. Xie, and N. Xu, Adv. Funct. Mater., 13, 487-492 (2003). C. Lai, X. P. Gao, B. Zhang, T. Y. Yan and Z. Zhou, J. Phys. Chem. C 113, 4712-4716 (2009). B. Zhang, C. Lai, Z. Zhou, and X.P. Gao, Electrochim. Acta, 54, 3708-3713 (2009). Y. A. Shahab, A. A. Siddiq, and K. S. Tawfiq, Carbon, 26, 801-802 (1988). J. Sun, Y. Huang, W. Wang, Z. Yu, A. Wang, K. Yuan, Electrochim. Acta, 53, 7084-7088 (2008). B. A. Trofimov, Sulfur Reports, 24, 283-305 (2003). W. Wei, J. Wang, L. Zhou, J. Yang, B. Schumann, Y. NuLi, Electrochem. Comm., 13, 399-402 (2011).

  The present invention enables the removal of unreacted sulfur from a product while sufficiently extracting the capacity of the organic sulfur-based positive electrode material in the production of the organic sulfur-based positive electrode material. An object of the present invention is to provide an apparatus capable of continuously and rapidly producing materials.

The present invention provides the following means in order to solve the above problems.
In the invention according to claim 1,
A raw material container for containing a raw material containing sulfur and organic matter;
A heating container for heating the raw material supplied from within the raw material container;
A product recovery container for recovering the product generated in the heating container;
A continuous transfer mechanism that continuously feeds the raw material supplied from the raw material container to the heating container and continuously sends the product generated in the heating container to the product recovery container;
A discharge pipe for taking out hydrogen sulfide generated in the heating vessel to the outside,
The exhaust pipe has a mechanism for condensing sulfur from the sulfur vapor and returning it to the heating vessel as a raw material as a processing mechanism for sulfur vapor contained in the exhaust gas discharged from the heating vessel; and Provided is an apparatus for continuously producing an organic sulfur-based positive electrode material for a secondary battery, which has at least one of mechanisms for discharging in a vapor state.

  According to this apparatus, a raw material containing sulfur and organic matter is continuously fed into a heating vessel by a continuous transfer mechanism, and sulfur and organic matter are reacted in the heating vessel to produce a product (organic sulfur-based positive electrode material). Thus, the produced product can be continuously sent out to the product collection container, and hydrogen sulfide generated in the heating container can be taken out from the discharge pipe to the outside. Moreover, it becomes possible to return the sulfur vapor contained in the exhaust gas discharged from the heating container into the heating container as a raw material and / or to discharge it outside as the steam. This provides a device that can synthesize and purify organic sulfur-based positive electrode materials in a rapid and large amount in a safe and environmentally friendly manner. Moreover, since this apparatus can perform the organic sulfur type positive electrode material from a laboratory scale production of several grams of prototypes to an industrial scale by simply changing the scale of the apparatus, it is highly versatile and convenient. .

In the invention according to claim 2,
A heating device for heating the discharge pipe;
The heating device may recycle sulfur as a raw material by liquefying sulfur vapor contained in the exhaust gas taken out from the heating vessel in the exhaust pipe and dripping the sulfur vapor toward the raw material in the heating vessel. The apparatus for continuously producing an organic sulfur-based positive electrode material for a secondary battery according to claim 1, wherein the discharge pipe is heated and controlled at a first heating temperature that can be produced.

  According to this apparatus, it is possible to prevent sulfur vapor contained in the exhaust gas taken out from the heating container from solidifying in the exhaust pipe and closing the exhaust pipe. Moreover, since sulfur vapor contained in the exhaust gas taken out from the heating vessel can be liquefied in the discharge pipe and dropped toward the raw material in the heating vessel, and the dropped sulfur can be reused as a raw material. A sufficient amount of raw material sulfur can be secured in the heating container, and the amount of sulfur used as the raw material can be reduced.

In the invention according to claim 3,
A heating device for heating the discharge pipe;
The heating device is configured to discharge the sulfur vapor contained in the exhaust gas taken out from the heating container at a second heating temperature at which the vapor can be taken out to the outside without being liquefied in the exhaust pipe. The apparatus for continuously producing an organic sulfur-based positive electrode material for a secondary battery according to claim 1, wherein the tube is heated and controlled.

  According to this apparatus, it is possible to prevent sulfur vapor contained in the exhaust gas taken out from the heating container from solidifying in the exhaust pipe and closing the exhaust pipe. Also, since sulfur vapor contained in the exhaust gas taken out from the heating vessel can be taken out in the state of vapor without being liquefied in the discharge pipe, there must be an excessive amount of sulfur in the heating vessel. And excessive sulfur can be prevented from adhering to the product.

In the invention according to claim 4,
A heating device for heating the discharge pipe;
The heating device may recycle sulfur as a raw material by liquefying sulfur vapor contained in the exhaust gas taken out from the heating vessel in the exhaust pipe and dripping the sulfur vapor toward the raw material in the heating vessel. The exhaust pipe is heated and controlled at a first heating temperature that can be obtained, and sulfur vapor contained in the exhaust gas taken out from the heating container is taken out to the outside in a vapor state without being liquefied in the exhaust pipe. 2. The organic battery for a secondary battery according to claim 1, wherein the discharge pipe is heated and controlled at a second heating temperature capable of switching between the first heating temperature and the second heating temperature. An apparatus for continuously producing a sulfur-based positive electrode material is provided.

  According to this apparatus, by switching the heating temperature of the exhaust pipe in accordance with the amount of sulfur present in the heating container, an excessive amount in the heating container is secured while securing a sufficient amount of raw material sulfur in the heating container. It is also possible to prevent the presence of sulfur.

In the invention according to claim 5,
The said exhaust pipe is connected with the said heating container in the position where the said liquefied sulfur is dripped toward an unreacted raw material, The organic sulfur type positive electrode material manufacturing apparatus for secondary batteries of Claim 2 characterized by the above-mentioned. ,I will provide a.

  According to this device, sulfur liquefied in the discharge pipe can be dropped toward the unreacted raw material in the heating vessel, so that the sulfur liquefied in the discharge pipe can be reliably used as the raw material. . It is also possible to prevent liquefied sulfur from adhering to the product.

In the invention according to claim 6,
6. The apparatus according to claim 1, further comprising an inert gas supply unit configured to supply an inert gas into the heating container from a downstream side to an upstream side in a transfer direction by the continuous transfer mechanism. An organic sulfur-based positive electrode material continuous production apparatus for secondary batteries is provided.

  According to this apparatus, excess sulfur vapor generated by heating from the crude product generated on the downstream side of the heating vessel is placed on the flow of the inert gas toward the raw material on the upstream side of the heating vessel. Can carry. Thereby, excess sulfur is removed (purified) from the crude product, and a high-capacity organic sulfur-based positive electrode material can be continuously synthesized.

In the invention according to claim 7,
The heating container is configured to be inclined or tiltable so that a downstream side in a transfer direction by the continuous transfer mechanism is higher than an upstream side. The organic sulfur type positive electrode material continuous manufacturing apparatus for secondary batteries as described is provided.

  According to this apparatus, it is prevented that the sulfur liquefied in the discharge pipe and dropped into the heating container flows down toward the downstream side of the heating container and adheres to the product.

  The invention according to claim 8 includes a sulfur recovery mechanism that recovers sulfur from hydrogen sulfide and sulfur vapor contained in the exhaust gas discharged from the exhaust pipe and discharges only hydrogen sulfide to the outside. An organic sulfur-based positive electrode material continuous production apparatus for a secondary battery according to any one of claims 1 to 7 is provided.

  According to this device, it is possible to recover sulfur from hydrogen sulfide and sulfur vapor contained in the exhaust gas discharged from the exhaust pipe and to discharge only hydrogen sulfide to the outside, so that sulfur can be reused. It becomes.

In the invention according to claim 9,
A heating reaction vessel for heating and reacting the raw material to produce a crude product; and for removing unreacted sulfur contained in the crude product produced in the heating reaction vessel. Consisting of a heated desulfurization vessel,
The continuous transfer mechanism continuously feeds the raw material supplied from the raw material container to the heated reaction vessel, and continuously transfers the crude product generated in the heated reaction vessel to the heated desulfurization vessel . The product produced in the heated desulfurization vessel is continuously sent out to the product recovery vessel. Organic sulfur-based positive electrode material continuous production for secondary battery according to any one of claims 1 to 8, Device.

According to this apparatus, a raw product can be reacted in a heated reaction vessel to produce a crude product, and unreacted sulfur can be removed from the crude product in a heated desulfurization vessel . In this way, by performing the production process and the desulfurization process in separate heating containers, heating conditions (temperature and time) suitable for each process can be set in each heating container. As a result, synthesis and desulfurization can be performed reliably, and the heating device can be reduced in size compared with the case where both processes are performed by one unit, and the load applied to a continuous transfer device such as a screw can be reduced. It becomes possible.

In the invention according to claim 10,
The said continuous transfer mechanism is a screw type, The organic sulfur type positive electrode material continuous manufacturing apparatus for secondary batteries in any one of the Claims 1 thru | or 9 provided.

  According to this apparatus, separation of the raw material and sulfur can be prevented by using a screw, and a sufficient amount of sulfur can be obtained by mixing the liquefied sulfur in the discharge pipe and dropping into the heating vessel with the raw material. It is possible to obtain the effect that the raw material can be spread and the vaporization of unreacted sulfur from the product can be promoted.

In the invention according to claim 11,
The continuous transfer mechanism is a roller hearth type, and provides an organic sulfur-based positive electrode material continuous production apparatus for a secondary battery according to any one of claims 1 to 9.

  According to this apparatus, the heating vessel containing the raw material in the furnace as a heating source is closely contacted and sent by a roller, and the sulfur is condensed from the sulfur vapor evaporated from the product and poured into the heating vessel immediately before the reaction. Thus, sufficient sulfur can be supplied. In addition, the length of the furnace is long enough to control the time and temperature enough to remove unreacted sulfur, and it is possible to process a larger amount of raw material than a screw, yet it is difficult to stir, and the highly viscous raw material Moreover, the effect that the hard organic sulfur type positive electrode material which consists of a hard product can be handled is acquired.

In the invention according to claim 12,
The continuous transfer mechanism is a pusher type, and provides an organic sulfur-based positive electrode material continuous production apparatus for a secondary battery according to any one of claims 1 to 9.

  According to this apparatus, the heating vessel containing the raw material in the furnace as the heating source is sent closely without gap, and the sulfur is condensed from the sulfur vapor evaporated from the product and poured into the heating vessel immediately before the reaction. Sufficient sulfur can be supplied. In addition, the length of the furnace is long enough to control the time and temperature enough to remove unreacted sulfur, and it is possible to process a larger amount of raw material than a screw, yet it is difficult to stir, and the highly viscous raw material Moreover, the effect that the hard organic sulfur type positive electrode material which consists of a hard product can be handled is acquired.

  According to the organic sulfur-based positive electrode material continuous production apparatus for secondary battery according to the present invention, a large amount of high-capacity organic sulfur-based positive electrode material can be continuously added while reliably and easily removing and purifying unreacted sulfur. Can be synthesized.

It is a schematic sectional drawing which shows the principal part of the organic sulfur type positive electrode material continuous manufacturing apparatus for secondary batteries which concerns on this invention. It is sectional drawing which shows the whole structure of the organic sulfur type positive electrode material continuous manufacturing apparatus for secondary batteries which concerns on this invention. It is sectional drawing which shows the whole structure of 2nd embodiment of the organic sulfur type positive electrode material continuous manufacturing apparatus for secondary batteries which concerns on this invention.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of an organic sulfur positive electrode material continuous production apparatus (hereinafter simply referred to as production apparatus) for a secondary battery according to the invention will be described with reference to the drawings as appropriate.
FIG. 1 is a schematic cross-sectional view showing the main part of the manufacturing apparatus according to the present invention, and FIG. 2 is a cross-sectional view showing the overall configuration of the manufacturing apparatus according to the present invention. FIG. 3 is a sectional view showing the overall configuration of the second embodiment of the manufacturing apparatus according to the present invention.
First, the manufacturing apparatus (first embodiment) shown in FIGS.

The production apparatus according to the present invention includes a raw material container (1) containing a raw material (M) containing sulfur and organic matter, a heating container (2) for heating a raw material supplied from within the raw material container (1), and a heating The product recovery container (3) for recovering the product generated in the container (2) and the raw material supplied from the raw material container (1) are continuously fed into the heating container (2) and the heating container (2 ) And a continuous transfer mechanism (4) for continuously sending the product generated in the product recovery container (3), and a discharge pipe for taking out hydrogen sulfide generated in the heating container (2) to the outside ( 5).
The discharge pipe (5) is a mechanism for returning sulfur into the heating vessel (2) as a raw material by condensing sulfur from the sulfur vapor as a processing mechanism for sulfur vapor contained in the exhaust gas discharged from the heating vessel (2). Mechanism) and a mechanism (discharge mechanism) for discharging sulfur vapor in a vapor state.

As shown in FIG. 1, the raw material container (1) preferably includes a stirring mechanism (6) for stirring and mixing the raw material (M). The stirring mechanism (6) includes a stirring blade (61) disposed in the raw material container (1) and a motor (62) that rotates the stirring blade (61).
The lower end discharge port of the raw material container (1) is connected in communication with one end side (upstream side) of the heating container (2). The raw material in the raw material container (1) is taken out from the lower end discharge port and supplied to one end side (upstream side) of the heating container (2). The lower end discharge port of the raw material container (1) and the one end side (upstream side) of the heating container (2) may be directly connected as shown in FIG. 1, or transferred by a screw conveyor or the like as shown in FIG. You may connect via a mechanism (10).

  The heating container (2) has a substantially cylindrical shape and is arranged with its central axis oriented sideways, and the lower end discharge port of the raw material container (1) is connected to one end side (upstream side) directly or via a transfer mechanism (10). Has been. The heating container (2) is attached with a continuous transfer mechanism (4) for continuously transferring the contents in the container along the axial direction from the upstream side to the downstream side. In the illustrated example, the continuous transfer mechanism (4) is a screw type mechanism (a screw conveyor provided with a screw (41) and a motor (42)). However, in the present invention, the configuration of the continuous transfer mechanism (4) is not particularly limited, and other types of continuous transfer mechanisms (not shown) such as a roller hearth type and a pusher type may be used.

  The heating container (2) has a heating part (8) heated by a heating source (7) and a non-heating part (9) that is not heated. The heating source (7) is composed of a heater of an electric furnace, for example, and is disposed on the outer periphery of the heating container (2). In addition, although the kind of heating source (8) is not specifically limited, since an electric furnace is used suitably, in the following description, a heating source may be demonstrated as an electric furnace (8).

  The heating container (2) has one end portion (upstream end portion) and the other end portion (downstream end portion) in the length direction as a non-heating portion (9), and an intermediate portion (one end portion and the other in the length direction). The heating section (8) is provided between the ends. A heating part (8) is provided over the range of about 70-80% of the whole length of a heating container (2), for example.

The heating temperature in the heating section (8) (the temperature inside the heating container (2)) is a temperature sufficient for sulfurization reaction between sulfur and organic matter contained in the raw material (preferably 300 to 450 ° C, more preferably 350 ° C). ˜420 ° C.) and kept constant.
The temperature in the heating container (2) is measured by a thermocouple (15), and is adjusted by controlling the electric furnace (8) with a temperature controller (not shown) based on the measured value.

  As the material of the heating vessel (2), it is preferable to use mullite, alumina, quartz, aluminum, and stainless steel for the part that comes into contact with the raw material containing liquid sulfur. From the viewpoint of properties, aluminum, quartz, or stainless steel is more preferable.

A discharge pipe (5) for taking out hydrogen sulfide and sulfur vapor generated in the heating container (2) is connected to the heating container (2). The discharge pipe (5) is connected to a position in the vicinity of the upstream end of the heating container (2). This connection position is a position where sulfur (described later) liquefied in the discharge pipe (5) can be dropped toward the unreacted raw material in the heating container (2). More specifically, it is a position immediately before the raw material is sent to the heating section (8), and is a position where the operating temperature is 150 ° C. to 200 ° C.
The discharge pipe (5) is preferably a pipe thicker than an inner diameter of 10 mmφ for the purpose of avoiding clogging with sulfur, and the periphery is heated by a heating device (11) such as a ribbon heater.

  The heating device (11) liquefies sulfur vapor contained in the exhaust gas taken out from the heating vessel (2) in the discharge pipe (5) and drops it toward the raw material in the heating vessel (2) to form sulfur. In the state of steam without liquefying the sulfur vapor contained in the exhaust gas taken out from the heating vessel (2) or the exhaust gas extracted from the heating vessel (2). The discharge pipe (5) is heated by the second heating temperature that can be taken out.

The first heating temperature is set to 100 ° C. or more and 200 ° C. or less. Thereby, it can prevent that sulfur vapor | steam solidifies in a discharge pipe (5), and obstruct | occludes a discharge pipe. Moreover, since sulfur vapor | steam can be liquefied in a discharge pipe (5), it is dripped toward the unreacted raw material in a heating container (2), and the dripped sulfur can be reused as a raw material, Therefore In this case, it is possible to secure a sufficient amount of raw material sulfur, and the amount of sulfur used as a raw material can be reduced.
Thus, the discharge pipe (5) functions as the return mechanism described above by being heated at the first heating temperature by the heating device (11).

The second heating temperature is set to 200 ° C. or higher. Thereby, it can prevent that sulfur vapor | steam solidifies in a discharge pipe (5), and obstruct | occludes a discharge pipe. Moreover, since it becomes possible to take out sulfur vapor | steam outside in the state of a vapor | steam, without making it liquefy in a discharge pipe (5), it can prevent that an excessive amount of sulfur exists in a heating container (2). it can.
When the first heating temperature is set when sulfur in the heating vessel (2) is excessive, sulfur vapor is liquefied and returned to the heating vessel (2), so that sulfur becomes excessive and excessive. Although the malfunction which sulfur adheres to a product may occur, since it will be taken out from a heating container (2) as a vapor | steam if it sets to 2nd heating temperature, generation | occurrence | production of this malfunction is prevented.
Thus, the discharge pipe (5) functions as the above-described discharge mechanism by being heated at the second heating temperature by the heating device (11).

  The heating device (11) preferably has a configuration capable of arbitrarily adjusting the heating temperature of the discharge pipe (5), and can be switched at least between the first heating temperature and the second heating temperature. It is preferable. With such a configuration, by switching the heating temperature of the exhaust pipe (5) in accordance with the amount of sulfur present in the heating vessel (2), a sufficient amount of raw material sulfur can be obtained in the heating vessel (2). It is possible to prevent an excessive amount of sulfur from being present in the heating container (2) while ensuring it. That is, when the amount of sulfur in the heating vessel (2) is insufficient, the first temperature is set to liquefy the sulfur vapor and drop it into the heating vessel (2), and conversely, the amount of sulfur is excessive. In this case, the sulfur vapor can be taken out by setting the second temperature.

A sulfur recovery container (13) is connected to the discharge side end of the discharge pipe (5), and exhaust gas such as sulfur vapor and hydrogen sulfide discharged from the heating container (2) is removed from the sulfur recovery container (13). Collected in. In addition, the inert gas supplied in the heating container (2) by the inert gas supply means (14) described later is also recovered in the sulfur recovery container (13).
The sulfur recovery container (13) preferably has a cooling means such as air cooling or water cooling. By cooling the sulfur recovery container (13) to a predetermined temperature (for example, 50 ° C.) or lower by cooling means, most of the sulfur is recovered in the sulfur recovery container (13), and only hydrogen sulfide and inert gas are discharged to the outside. It becomes possible to do. That is, the sulfur recovery container (13) and its cooling means function as a sulfur recovery mechanism. Hydrogen sulfide that is not recovered in the sulfur recovery container (13) is converted to sulfur oxide having low toxicity using a combustor or the like and is removed by absorption in water.

  The raw materials accommodated in the heating container (2) from the raw material container (1) are organic substances such as polyacrylonitrile (PAN), coal pitch, rubber, paraffins, activated carbon, acetylene black, bitumen, gelatin, polyethylene resin, acrylic resin, etc. It is a mixture of 120 to 600 parts by mass (preferably 140 to 200 parts by mass) of sulfur with respect to parts by mass. Although the mixing method is not particularly limited, for example, mixing can be performed using a general mixing device such as a mortar or a ball mill. Moreover, you may mix | blend the general material (conductive auxiliary agent etc.) which can be mix | blended with the positive electrode active material of a secondary battery as needed. The form of the raw material may be powdery or may be formed into a pellet or the like, and is not particularly limited.

  This raw material is continuously transferred to the heating section (8) by the continuous transfer mechanism (4) and heated at 250 to 500 ° C., preferably 300 to 450 ° C., more preferably 350 to 420 ° C. Causes sulfurization reaction with organic matter. When this sulfidation reaction (sulfurization heat treatment step) is performed in a non-oxidizing atmosphere, when the organic substance is PAN, simultaneously with the PAN ring-closing reaction, the vapor form sulfur reacts with PAN and is modified by sulfur. Is obtained. Here, the non-oxidizing atmosphere includes a depressurized state having a low oxygen concentration such that the oxidation reaction does not proceed, an inert gas atmosphere such as nitrogen or argon, a sulfur gas atmosphere, and the like.

During the sulfurization reaction between sulfur and organic matter, a large amount of sulfur vapor is generated because the reaction temperature is sufficiently higher than the temperature at which sulfur evaporates.
In a moving bed reaction apparatus used industrially or in a normal heating reaction vessel such as a rotary kiln, sulfur quickly escapes from the reaction system and cannot sufficiently react with organic matter. In addition, even when mixed raw materials are placed in a crucible or the like having a length to diameter ratio of 3: 1 or less and reacted in an atmospheric furnace, the evaporated sulfur does not return to the reaction system, so that sulfur is insufficient and organic sulfur has good characteristics. It is difficult to reliably obtain a positive electrode material.
On the other hand, according to the production apparatus according to the present invention, inside the heating vessel (2), the raw material is moved in the heating vessel (2) while being stirred in a dense state by the continuous transfer mechanism (4), or in the reaction. Since sulfur that has not been used and has adhered to the product is vaporized and supplied to the raw material together with heat, the reaction is carried out in an environment where necessary and sufficient sulfur is present. Further, even when sulfur vapor vaporized by heating is discharged through the discharge pipe (5), the sulfur vapor is condensed as liquid sulfur in the discharge pipe (5) and dropped into the raw material, and again subjected to the sulfurization reaction as the sulfur raw material. (In other words, the evaporated sulfur can be returned to the raw material as a liquid), so that the problem of sulfur shortage does not occur.

The heating container (2) is inclined about 1 to 2 degrees with respect to the horizontal direction so that the downstream side in the transfer direction by the continuous transfer mechanism (4) is higher than the upstream side (raw material supply side) or It is preferable to be configured to be tiltable. In this configuration, the length of the plurality of legs (12) that support the gantry on which the heating container (2) is placed and fixed can be set to an appropriate length in advance or can be adjusted to an appropriate length. Can be realized.
By comprising in this way, it is prevented that the liquid sulfur dripped toward the inside of the heating container (2) flows down toward the downstream side of the heating container (2) and adheres to the product.

The manufacturing apparatus according to the present invention includes an inert gas supply means for supplying an inert gas (nitrogen gas, argon gas, etc.) into the heating vessel (2). The inert gas supply means includes an inert gas supply pipe (14) connected to an inert gas storage container (not shown) and the like, and the heating container (2) from the downstream side to the upstream side in the transfer direction. An inert gas is circulated inside. The arrows in FIG. 1 indicate the gas flow direction. In the figure, nitrogen gas (N ₂ ) is shown as an example of the inert gas.
By providing the inert gas supply means, excess sulfur vapor generated by heating from the crude product (product containing unreacted sulfur) generated on the downstream side of the heating vessel (2) is removed from the inert gas. It can be carried in the direction of the raw material upstream of the heating vessel. Thereby, excess sulfur is removed (purified) from the crude product, and a high-capacity organic sulfur-based positive electrode material can be continuously synthesized.

  The raw material supplied from the raw material container (1) into the heating container (2) reacts by being heated in the heating section (8), and first a crude product (product containing unreacted sulfur) is obtained. Then, the unreacted sulfur is removed by further heating the crude product, and the target product (organic sulfur-based positive electrode material for secondary battery) is obtained.

  The reaction time in the heating vessel (2) is defined by the time required to pass through the heating section (8), and is preferably about 10 minutes in which sulfur is sufficiently vaporized and removed from the crude product. The reaction is completed at about 300 ° C., which is lower than the set temperature 350 ° C. to 420 ° C. of the heating vessel (2). After reaching that temperature, unreacted sulfur is vaporized from the crude product, A product from which unreacted sulfur has been removed is obtained.

The unreacted sulfur vapor removed from the crude product by heating is carried away by the inert gas supplied from the inert gas supply means (14). This ensures that the crude product is purified with unreacted sulfur removed. The flow rate of the inert gas is 100 to 500 ml per minute, more preferably 200 to 300 ml per minute per 10 cm ² of the cross section of the heating container (2). As shown in the figure, an inert gas (nitrogen gas, argon gas, etc.) is preferably supplied above the reaction vessel (2) (above the product). The reason for this is that the inert gas is lighter than hydrogen sulfide and sulfur vapor, so that the inert gas is supplied from above the reaction vessel (2), so that the sulfur vapor and sulfide generated from the product and accumulated upward This is because hydrogen can be efficiently transported to the raw material side and the discharge pipe (5).

  The product (organic sulfur-based positive electrode material for secondary battery) obtained by removing unreacted sulfur from the crude product is easily peeled off from the continuous transfer mechanism (4) (for example, screw), It is sent out from a heating container (2), and is collect | recovered in the product collection container (3) connected to the downstream edge part of a heating container (2).

  Next, based on FIG. 3, a different point from 1st embodiment is demonstrated about 2nd embodiment of the manufacturing apparatus which concerns on this invention. In FIG. 3, the same reference numerals are given to the same (corresponding) configurations as in the first embodiment.

  In the production apparatus of the second embodiment, the heating container (2) is generated by a heating reaction container (21) for heating and reacting the raw materials to produce a crude product, and a heating reaction container (21). The main feature is that it is composed of two containers, a heated desulfurization container (22) for removing unreacted sulfur contained in the crude product.

The continuous transfer mechanism (4) continuously feeds the raw material supplied from the raw material container (1) into the heating reaction container (21) and converts the crude product generated in the heating reaction container (21) into the heating reaction container. The first transfer mechanism (4A) continuously fed from (21) and the crude product sent from the heated reaction vessel (21) are continuously fed into the heated desulfurization vessel (22) and heated desulfurization vessel ( 22) It consists of the 2nd transfer mechanism (4B) which sends out the product produced | generated in the product collection container (3) continuously. Each transfer mechanism is shown as a screw type in the figure, but may be a roller hearth type or a pusher type.

The heating reaction vessel (21) and the heating desulfurization vessel (22) have the same structure as the heating vessel (2) of the first embodiment, but each vessel (21) (22) has a different heating temperature. . The heating temperature of the heating reaction vessel (21) is set to a temperature (for example, 350 to 420 ° C.) suitable for generating a crude product by reacting the raw materials, and the heating temperature of the heating desulfurization vessel (22) is And a temperature suitable for removing unreacted sulfur from the crude product (for example, 250 to 320 ° C.).

The discharge pipe (5) includes a first discharge pipe (5A) provided on the upstream side of the heating reaction container (21) and a second discharge pipe (5B) provided on the downstream side of the heating reaction container (21). ) And a third discharge pipe (5C) provided on the upstream side of the heat desulfurization vessel (22).
Each discharge pipe (5A) (5B) (5C) is heated by the heating device (11) at the first heating temperature or the second heating temperature, respectively. From the discharge pipes (5A), (5B), and (5C), sulfur vapor, hydrogen sulfide, and inert gas in the heated reaction vessel (21) and the heated desulfurization vessel (22) are discharged.

The inert gas supply means is connected to the heated desulfurization vessel (22) from the downstream side to the upstream side in the transfer direction via the inert gas supply pipe (14) connected to the downstream end of the heated desulfurization vessel (22). ) To the heated reaction vessel (21).

The raw material supplied from the raw material container (1) into the heated reaction container (21) is heated to react to obtain a crude product (a product containing unreacted sulfur). The obtained crude product is continuously sent to the heated desulfurization vessel (22), and further heated to remove unreacted sulfur contained in the crude product, whereby the desired product ( Organic sulfur-based positive electrode material for secondary battery) is obtained. The obtained product is continuously fed into the product recovery container (3) connected to the downstream end of the heat desulfurization container (22) and recovered.

According to this apparatus, the raw material is reacted in the heated reaction vessel (21) to produce a crude product, and the unreacted sulfur is removed (purified) from the crude product in the heated desulfurization vessel (22). Can do. In this way, by performing the production process and the desulfurization process in separate heating vessels ((21) and (22)), heating conditions (temperature and time) suitable for each process are set in each heating vessel. be able to. As a result, desulfurization can be performed reliably, the heating device can be made smaller than when both processes are performed by one unit, and the load applied to the continuous transfer mechanism such as a screw can be reduced. Become.

  Hereinafter, the effect of the present invention will be clarified by showing examples and comparative examples of the present invention. However, the present invention is not limited to the following examples.

<Example 1>
(Manufacture of organic sulfur-based positive electrode materials for secondary batteries)
1. Preparation of raw material A raw material was prepared by mixing 10.0 g of polyacrylonitrile powder and 14.12 g of sulfur (99.9%, manufactured by Hosoi Chemical).

2. An apparatus transparent quartz tube (inner diameter 45 mmφ, outer diameter 50 mmφ, length 500 mm) was used as a heating container. Both ends of this quartz tube were fastened with silicone rubber stoppers, and an 8 mmφ gas inlet and a gas outlet were perforated in each rubber stopper. A stainless bar (made of SUS316, diameter 5 mmφ, length 600 mm) was welded with a screw cut from a stainless steel plate and bent and attached to the stainless rod (screw diameter 42 mmφ, screw length 450 mm). A hole was drilled in the center of a silicone rubber stopper attached to one side of the quartz tube, and a screw rod was attached. A continuous transfer mechanism was constructed by attaching a handle for rotating a screw to a stainless steel rod that was exposed outside the quartz tube.
A quartz tube with a screw attached inside was placed in a tubular electric furnace (heating source) so that both ends of the quartz tube would go out of the furnace. The electric furnace and the quartz tube were fixed to an aluminum frame using a jig. A block was placed under the frame so that the end (upstream end) of the quartz tube on the side where the raw material was placed was lowered with an inclination of 1 to 2 degrees with respect to the other end (downstream end).
A fluororesin tube (discharge tube) was attached to the gas outlet of the quartz tube, and a ribbon heater (60 cm) was wound around it, and the temperature was controlled to 150 ° C. with a temperature controller. From there, a polyethylene tube connected to an Erlenmeyer flask prepared for collecting hydrogen sulfide was connected. Two fluororesin tubes (outer diameter: 6.3mmφ, inner diameter: 3mmφ, length: 150mm) are attached by drilling two holes in a silicone rubber stopper, and three sets of them are attached to three Erlenmeyer flasks (each volume 500ml) It was. About 100 ml of an alkaline aqueous solution in which 40 g of sodium hydroxide was dissolved in 300 ml of water was poured into each Erlenmeyer flask. Connect the polyethylene pipe (outer diameter 8mmφ, inner diameter 6mmφ, length 500mm) to the exhaust gas port protruding from the quartz tube, connect it to one of the two fluororesin tubes of the Erlenmeyer flask, and another triangle from the other fluororesin tube A polyethylene tube was connected to the flask, and a polyethylene tube was piped so that the gas passed through the three Erlenmeyer flasks in series. The first of the three Erlenmeyer flasks does not immerse the fluororesin tube in the alkaline aqueous solution, and in the remaining two Erlenmeyer flasks, the exhaust gas is bubbled by immersing the tube containing the gas in the alkaline aqueous solution. Hydrogen sulfide can be collected.
A fluororesin tube (inert gas supply tube) was attached to the gas inlet of the quartz tube, and nitrogen gas was fed into the quartz tube from there.

3. The mixed raw material for the sulfidation heat treatment and sulfur removal process was put in a quartz tube, and the electric furnace temperature was set to 420 ° C. Nitrogen gas was flowed every 300 ml from the opposite side of the raw material. The handle of the screw was manually rotated half a minute to feed the raw material into the part of the quartz tube heated by the electric furnace (heating part). When the raw material was fed into the heating section, hydrogen sulfide was generated from the heated raw material. In the conventional apparatus, the generated hydrogen sulfide is exhausted from the exhaust port containing sulfur, and there is a problem that the narrow exhaust port is easily blocked by the adhesion of sulfur. However, in this apparatus, it was observed that liquefied sulfur dropped into the raw material and was mixed with the raw material. Further, since the discharge pipe was heated, the discharge pipe was not blocked with sulfur. Moreover, in this apparatus, it was confirmed by the discoloration (due to the molten sulfur) of the raw material before entering the heating section that the heat in the exhaust gas was also absorbed and reused by the raw material.
The airtightness of the device was good, and the generated hydrogen sulfide did not leak outside the quartz tube.
After 13 minutes, the product was sent out of the electric furnace (heating section). This was followed by 13.67 g of product in 13 minutes. Sulfur was removed by heating with an electric furnace and a stream of nitrogen gas, and a purified product could be obtained. The removed sulfur was transferred to subsequent raw materials and used for the reaction.

<Comparative Example 1>
(Synthesis using rotary kiln)
1. Preparation of raw material A mixture of 5 g of polyacrylonitrile powder and 17.5 g of sulfur (Kishida Chemical, 99%) was used as a raw material.

2. A rotary kiln used in a general synthesis method for firing the apparatus raw material evenly while rotating was used.
A quartz tube container (cylindrical, inner diameter 74 mmφ, outer diameter 80 mmφ, length 180 mm, quartz plates each having an opening of 30 mmφ on each side) was used as a heating vessel, and raw materials were put into this vessel. This container was placed in a quartz core tube that rotates horizontally once per minute so that two openings are in the same direction as the core tube. A vinyl tube was connected to the gas outlet between the cores, and this tube was immersed in an Erlenmeyer flask containing an alkaline aqueous solution of 40 g of sodium hydroxide dissolved in 300 ml of water so that the exhaust gas was bubbled. The suction port of the activated carbon absorber was installed at the outlet of the Erlenmeyer flask to collect the hydrogen sulfide that could not be collected and send the exhaust to the outdoors.

3. Nitrogen gas was allowed to flow at 100 ml / min in the heating vessel for the sulfidation heat treatment step , and the temperature was raised to 400 ° C. over 1 hour.
After the temperature reached 400 ° C., the temperature was lowered and the product was removed. The product obtained was 6.4 g. If the positive electrode active material sufficiently contains sulfur, a mass of 8 g can be expected, but the product is deficient in sulfur, the properties are different from the original fine powder, and the particles are aggregated. This is probably because most of the sulfur used had flew away before 350 ° C, the appropriate temperature for the reaction. Furthermore, it was difficult to clean the core tube to which sulfur adhered after the reaction.

<Comparative example 2>
(Small batch synthesis)
1. Preparation of raw material A mixture of 20 g of polyacrylonitrile powder and 70 g of sulfur (Aldrich, 99.9%) in a mortar was used as a raw material.

2. A quartz tube (inner diameter 60 mmφ, length 380 mm) with the lower part of the apparatus closed in a hemispherical shape was used as a heating container, and the raw material was placed in the bottom of the quartz tube. To the lid of this container, a silicone rubber stopper (No. 15) with two holes of 8 mmφ and one hole of 6 mmφ was attached with a cork borer. Attached to this is an alumina tube with a closed end (made by Nikkato, material SSA-S, outer 6mmφ, inner diameter 4mmφ, length 400mm), a K-type thermocouple is placed inside this alumina tube, the raw material temperature is measured, The furnace was used for temperature control. Separately, two alumina tubes (manufactured by Nikkato, material SSA-S, outer 8 mmφ, inner diameter 5 mmφ, length 80 mm) were pierced into the above-mentioned silicone rubber stoppers to form a nitrogen introduction tube and an exhaust tube, respectively.
Two fluororesin tubes (outer diameter 8 mm, inner diameter 6 mm, length 150 mm) are attached by drilling two holes in a silicone rubber stopper, and three sets of these are attached to three Erlenmeyer flasks (each volume 500 ml) It was. About 100 ml of an alkaline aqueous solution in which 20 g of sodium hydroxide was dissolved in 300 ml of water was poured into each Erlenmeyer flask. Connect the silicone rubber pipe (10mmφ, inner diameter 8mmφ, length 50cm) to the exhaust port protruding from the quartz tube, connect the other end to the two fluororesin tubes of the Erlenmeyer flask, and another Erlenmeyer flask from the other fluororesin tube The silicone rubber tube was connected to the tube, and the silicone rubber tube was piped so that the gas passed through the three Erlenmeyer flasks in series. In each of the three Erlenmeyer flasks, the tubes containing the gas were immersed in an alkaline aqueous solution, and the exhaust gas was bubbled so that hydrogen sulfide could be collected.

3. Sulfidation heat treatment process 100 ml of nitrogen gas was fed into the quartz tube for 2 hours to perform gas replacement, and the nitrogen inflow tube was closed by the pinchcock Hoffman method. The quartz tube was placed in an electric furnace and heated up to 250 mm from the bottom of the quartz tube.
After 20 minutes from the heating, when the temperature of the raw material reached 180 ° C., a large amount of hydrogen sulfide gas was generated and an odor began to appear. Hydrogen sulfide permeated through the silicone rubber tube, and when the detector was brought close to it, the surface showed 10 ppm. The generation of hydrogen sulfide gas became noticeable at 240 ° C, and a large amount of sulfur adhered to the upper part of the quartz tube. Immediately after, the sulfur closed the outlet pipe, and the pressure of hydrogen sulfide gas accumulated in the quartz tube caused the silicone rubber stopper to come off the quartz tube, causing hydrogen sulfide to leak, and the hydrogen sulfide detector sounded an alarm exceeding 20 ppm. A gas mask was used to remove the sulfur in the blockage, and the silicone rubber stopper was fitted into the quartz tube to continue the operation. Hydrogen sulfide leaking into the room was sucked through a duct and exhausted outdoors. After stopping the heating of the electric furnace at 380 ° C, when the raw material temperature no longer rises above 420 ° C, take out the quartz tube from the electric furnace, lie down on the quartz cotton and cool it down, and the condensed sulfur is coarse. The quartz tube was tilted down and cooled to keep the crude product high so that it did not flow down into the product. The obtained crude product was 60 g of a brittle mass.

4). Purification process (single sulfur removal process)
The obtained crude product contains a large amount of elemental sulfur because sulfur was not removed, and cannot be used as a positive electrode material as it is. For this reason, the lump was pulverized, and 2 g each was heated in a vacuum processing vessel under vacuum at 250 ° C. for 2 hours to remove sulfur. About 1 g of organic sulfur-based positive electrode material was obtained from 2 g of the crude product.

<Summary of Examples and Comparative Examples>
As described above, according to the example (the present invention), a high-capacity organic sulfur-based positive electrode material from which unreacted sulfur is continuously removed in a short time can be efficiently synthesized using a minimum amount of sulfur. I was able to.
On the other hand, in the comparative example, it is not possible to continuously synthesize in a short time, and additionally, a heat treatment under vacuum is separately required for removing unreacted sulfur, and a high-capacity organic sulfur-based positive electrode material Could not be synthesized efficiently.

  Hereafter, the test example which confirmed the performance as a positive electrode active material of a lithium ion secondary battery about the organic sulfur type positive electrode material obtained in Example 1 and Comparative Examples 1 and 2 is shown.

<Test example>
1. Electrode fabrication
The resulting organic sulfur-based positive electrode material 3.0mg, PTFE (polytetrafluoroethylene) 0.3mg and acetylene black 2.7mg were kneaded by hand until using agate mortar to form a sheet, and a disk shape with a diameter of about 10mm. The shape was adjusted so that The obtained disc-shaped electrode sheet is placed on an aluminum mesh (# 100 mesh) punched out into a circle with a diameter of 13 mm, and is pressed and integrated with a desktop hand press at a pressure of 20 MPa. As a result, a positive electrode was produced. The aluminum mesh is a current collector that plays a role of increasing the current collecting performance of the electrode. On the other hand, metallic lithium having a diameter of 13 mm and a thickness of 0.5 mm was used for the negative electrode.

2. Battery production
A 2032 type coin battery was assembled as a battery for evaluation. A polypropylene microporous membrane (Celgard 2400, manufactured by Celgard) was used as the separator. The electrolyte used was a mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1 and LiPF ₆ (lithium hexafluorophosphate) dissolved to a concentration of 1 mol / L. .
According to a conventional method, the positive electrode using the above-mentioned organic sulfur-based positive electrode material and the lithium metal negative electrode are opposed to each other, and a separator impregnated with an electrolytic solution is sandwiched therebetween so that the two are not in direct contact with each other. A battery was produced by placing it in a battery can together with a leaf spring, placing a lid, and crimping and sealing the battery can and lid.

3. Charge / discharge test
A charge / discharge test was performed on the manufactured battery. The current density during the charge / discharge test was 60 mA / g. This is because when the organic sulfur-based positive electrode material has an electric capacity of 600 mAh / g, the test is performed at a sufficiently slow charge / discharge rate that is charged or discharged over 10 hours. When the current value is increased, when the resistance is large, the original electric capacity may not be exhibited. Therefore, a test at a slow charge / discharge rate was performed. The voltage range is 1.0 to 3.0V vs. Tests were performed with Li ⁺ / Li. The test temperature was 30 ° C.
The results of the charge / discharge test are shown in Table 1.

4). Battery evaluation results
As shown in Table 1, in Examples using the organic sulfur-based positive electrode material obtained by the apparatus of the present invention, as a positive electrode material of a lithium ion secondary battery, 250 mAh / A large electric capacity of g or more was obtained.
In addition, when the organic sulfur type positive electrode material obtained by the apparatus of Comparative Example 1 was used, only a small electric capacity was obtained. This is because an apparatus using a rotary kiln could not incorporate a sufficient amount of sulfur into the product. Further, the apparatus of Comparative Example 2 is not suitable for synthesizing a large amount of organic sulfur-based positive electrode material because it requires a separate heat treatment under vacuum in order to remove unreacted sulfur.
From this, the apparatus of the present invention is capable of synthesizing organic sulfur-based positive electrode materials capable of obtaining a large charge / discharge capacity continuously and quickly in large quantities in consideration of safety and the environment. It can be said that it is an excellent device.

  The present invention is mainly used for continuously producing an organic sulfur-based active material useful as a positive electrode active material for lithium ion or sodium ion secondary batteries.

Claims (12)

A raw material container for containing a raw material containing sulfur and organic matter;
A heating container for heating the raw material supplied from within the raw material container;
A product recovery container for recovering the product generated in the heating container;
A continuous transfer mechanism that continuously feeds the raw material supplied from the raw material container to the heating container and continuously sends the product generated in the heating container to the product recovery container;
A discharge pipe for taking out hydrogen sulfide generated in the heating vessel to the outside,
The exhaust pipe has a mechanism for condensing sulfur from the sulfur vapor and returning it to the heating vessel as a raw material as a processing mechanism for sulfur vapor contained in the exhaust gas discharged from the heating vessel; and An apparatus for continuously producing an organic sulfur-based positive electrode material for a secondary battery, comprising at least one of mechanisms for discharging in a vapor state. A heating device for heating the discharge pipe;
The heating device may recycle sulfur as a raw material by liquefying sulfur vapor contained in the exhaust gas taken out from the heating vessel in the exhaust pipe and dripping the sulfur vapor toward the raw material in the heating vessel. The apparatus for continuously producing an organic sulfur-based positive electrode material for a secondary battery according to claim 1, wherein the discharge pipe is heated and controlled at a first heating temperature that can be produced. A heating device for heating the discharge pipe;
The heating device is configured to discharge the sulfur vapor contained in the exhaust gas taken out from the heating container at a second heating temperature at which the vapor can be taken out to the outside without being liquefied in the exhaust pipe. 2. The apparatus for continuously producing an organic sulfur-based positive electrode material for a secondary battery according to claim 1, wherein the tube is heated and controlled. A heating device for heating the discharge pipe;
The heating device may recycle sulfur as a raw material by liquefying sulfur vapor contained in the exhaust gas taken out from the heating vessel in the exhaust pipe and dripping the sulfur vapor toward the raw material in the heating vessel. The exhaust pipe is heated and controlled at a first heating temperature that can be obtained, and sulfur vapor contained in the exhaust gas taken out from the heating container is taken out to the outside in a vapor state without being liquefied in the exhaust pipe. second the discharge pipe at a heating temperature heating control, and the first organic for a secondary battery according to claim 1, wherein the heating temperature is switchable between said second heating temperature which can Sulfur-based positive electrode material continuous production equipment.   The said exhaust pipe is connected with the said heating container in the position where the said liquefied sulfur is dripped toward an unreacted raw material, The organic sulfur type positive electrode material manufacturing apparatus for secondary batteries of Claim 2 characterized by the above-mentioned. .   6. The apparatus according to claim 1, further comprising an inert gas supply unit configured to supply an inert gas into the heating container from a downstream side to an upstream side in a transfer direction by the continuous transfer mechanism. An organic sulfur-based positive electrode material continuous production system for secondary batteries.   The heating container is configured to be inclined or tiltable so that a downstream side in a transfer direction by the continuous transfer mechanism is higher than an upstream side. The organic sulfur type positive electrode material continuous manufacturing apparatus for secondary batteries as described.   8. A sulfur recovery mechanism for recovering sulfur from hydrogen sulfide and sulfur vapor contained in the exhaust gas discharged from the exhaust pipe and discharging only hydrogen sulfide to the outside. The organic-sulfur-type positive electrode material continuous manufacturing apparatus for secondary batteries as described in 1 above. A heating reaction vessel for heating and reacting the raw material to produce a crude product; and for removing unreacted sulfur contained in the crude product produced in the heating reaction vessel. Consisting of a heated desulfurization vessel,
The continuous transfer mechanism continuously feeds the raw material supplied from the raw material container to the heated reaction vessel, and continuously transfers the crude product generated in the heated reaction vessel to the heated desulfurization vessel . The product produced in the heated desulfurization vessel is continuously sent out to the product recovery vessel. Organic sulfur-based positive electrode material continuous production for secondary battery according to any one of claims 1 to 8, apparatus.   The said continuous transfer mechanism is a screw type, The organic sulfur type positive electrode material continuous manufacturing apparatus for secondary batteries in any one of the Claims 1 thru | or 9 characterized by the above-mentioned.   The apparatus for continuously producing an organic sulfur-based positive electrode material for a secondary battery according to any one of claims 1 to 9, wherein the continuous transfer mechanism is a roller hearth type.   The said continuous transfer mechanism is a pusher type, The organic sulfur type positive electrode material continuous manufacturing apparatus for secondary batteries in any one of the Claims 1 thru | or 9 characterized by the above-mentioned.

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