Sintering equipment for preparing solid electrolyte

Abstract

The utility model relates to the technical field of all-solid-state batteries, in particular to sintering equipment for preparing solid electrolyte, a first sagger transportation channel is arranged in a push plate furnace, and a feeding glove box and a discharging glove box are respectively communicated with a feeding end and a discharging end of the first sagger transportation channel in a sealing manner; a feeding gate valve is arranged at the feeding end of the first sagger conveying channel, and a discharging gate valve is arranged at the discharging end of the first sagger conveying channel. A roller way is arranged in the first sagger conveying channel, an air inlet is formed in the feeding end of the first sagger conveying channel and connected with an inert atmosphere source, and an air outlet is formed in the discharging end of the first sagger conveying channel; the discharging end of the first sagger conveying channel communicates with a plurality of condensation collectors. The continuous sintering device has the beneficial effects that the continuous sintering of the sulfide solid electrolyte can be realized, the product quality, the preparation efficiency and the production safety are obviously improved, the maintenance cost is reduced, and the batch consistency is improved.

Description

TECHNICAL FIELD

[0001] The utility model relates to all solid state battery technical field especially relates to a kind of sintering equipment for preparing solid electrolyte. BACKGROUND

[0002] As the next generation battery technology that can realize high energy density and high safety, all-solid-state battery is the inevitable development trend of lithium-ion battery. Among them, sulfide system all-solid-state battery is considered as the most potential technology route, and it is focused by global major enterprises in this field. One of the core problems of this technology route is how to realize large-scale preparation of sulfide solid electrolyte, and the difficulty mainly lies in that sulfide solid electrolyte and its raw materials for preparation are extremely sensitive to air, and have high requirements on preparation process and equipment. Among them, high-temperature sintering is the most core process step, and raw materials undergo solid-phase chemical reaction in this process step to generate sulfide solid electrolyte. The sintering equipment used in this process step not only needs to resist sulfide corrosion, but also has high requirements on temperature control accuracy, temperature field uniformity, airtightness and other performance indicators.

[0003] Although there are various sintering equipment in the current market, most of them are traditional equipment for traditional industry and traditional material, and they cannot match the mass production of sulfide solid electrolyte in terms of mechanical structure, key component material, automation / continuity degree and the like. UTILITY MODEL CONTENT

[0004] The technical problem to be solved by the utility model is to provide a sintering equipment for preparing solid electrolyte to solve the above problems existing in the prior art.

[0005] The technical solution for solving the above technical problem of the utility model is as follows: a sintering equipment for preparing solid electrolyte, comprising a feeding glove box, a push plate furnace and a discharging glove box, a first sagger conveying passage is arranged in the push plate furnace, the feeding glove box is in sealed communication with the feeding end of the first sagger conveying passage, and the discharging glove box is in sealed communication with the discharging end of the first sagger conveying passage; a feeding plug valve is arranged at the feeding end of the first sagger conveying passage, and a discharging plug valve is arranged at the discharging end of the first sagger conveying passage; a roller bed for conveying sagger along the length direction of the first sagger conveying passage is arranged in the first sagger conveying passage, an air inlet is arranged at the feeding end of the first sagger conveying passage, an inert atmosphere gas source is connected to the air inlet, and an air outlet is arranged at the discharging end of the first sagger conveying passage; a plurality of condensation collectors are communicated with the discharging end of the first sagger conveying passage; a heating mechanism for segmentally heating the inside of the first sagger conveying passage is arranged in the push plate furnace.

[0006] The sulfide solid electrolyte can be continuously sintered, product quality, preparation efficiency and production safety are improved, maintenance cost is reduced, and batch consistency is improved.

[0007] Based on the above technical scheme, the utility model further can make improvement as follows.

[0008] Further, the input end of the condensation collector is communicated with the side wall of the discharge end of the first saggar conveying channel, and the output end of the condensation collector is connected with the input end of the sulfur-containing tail gas absorption device through an exhaust pipe.

[0009] The sulfur-containing tail gas absorption device is arranged to absorb the sulfide volatilization that fails to be condensed, and personnel safety and environmental protection problems are solved.

[0010] Further, the output end of the sulfur-containing tail gas absorption device is connected with a hydrogen sulfide detector.

[0011] The hydrogen sulfide detector is arranged to monitor the hydrogen sulfide gas in the tail gas purified by the sulfur-containing tail gas absorption device in real time, and the hydrogen sulfide gas is prevented from being discharged.

[0012] Further, the first saggar conveying channel is provided with a water / oxygen detection probe for detecting the water / oxygen concentration of the feeding end.

[0013] The water / oxygen detection probe can detect the water / oxygen concentration of the feeding end of the first saggar conveying channel.

[0014] Further, the first saggar conveying channel is provided with a pressure sensor for detecting the internal pressure.

[0015] The pressure sensor is arranged to monitor the pressure in the first saggar conveying channel, and the abnormal increase of the furnace pressure is avoided.

[0016] Further, the first saggar conveying channel is provided with a plurality of temperature detection mechanisms for detecting the temperature of each temperature zone.

[0017] The temperature detection mechanisms are arranged to detect the real-time temperature of each temperature.

[0018] Further, the temperature detection mechanisms adopt S-type thermocouples made of platinum-rhodium alloy or K-type thermocouples with ceramic layers on surfaces.

[0019] The above further scheme can prevent the temperature measurement from being inaccurate due to corrosion.

[0020] Further, the heating mechanism comprises an electric heating assembly and a graphite rod, the graphite rod is arranged in the first saggar conveying channel, and the electric heating assembly is electrically connected with the graphite rod.

[0021] The beneficial effect of the further scheme is that the atmosphere containing corrosive volatile matters will not corrode the graphite rod, the non-uniform temperature field caused by corrosion of the heating component is prevented, and the cost of consumables is reduced.

[0022] Further, the heating mechanism comprises an alloy heating wire, the alloy heating wire is arranged in the first saggar conveying channel, and the alloy heating wire is sleeved with a graphite shell layer or a quartz sleeve.

[0023] The beneficial effect of the further scheme is that the general alloy heating wire is protected by the quartz sleeve, or the alloy heating wire is isolated from the atmosphere containing corrosive volatile matters by the graphite shell layer, the non-uniform temperature field caused by corrosion of the heating component is prevented, and the cost of consumables is reduced.

[0024] Further, the gas inlet is connected with a sintering aid input source.

[0025] The beneficial effect of the further scheme is that the sintering aid can help sintering. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 It is a top view structural schematic diagram of an embodiment of the utility model;

[0027] Figure 2 It is a sectional view schematic diagram of the discharge end of the first saggar conveying channel in the embodiment of the utility model;

[0028] In the drawings, the component list represented by each sign is as follows:

[0029] 1, feed glove box; 2, push plate furnace; 3, discharge glove box; 4, first saggar conveying channel; 5, feed plug valve; 6, discharge plug valve; 7, saggar; 8, roller way; 9, gas inlet; 10, gas outlet; 11, condensation collector; 12, sulfur-containing tail gas absorption device; 13, hydrogen sulfide detector; 14, water oxygen detection probe; 15, pressure sensor; 16, condensation plug valve; 17, control and feedback system; 18, exhaust pipe; 19, second saggar conveying channel. DETAILED DESCRIPTION

[0030] The principles and characteristics of the utility model are described below in combination with the drawings, and the examples are only used to explain the utility model and are not used to limit the scope of the utility model.

[0031] As Figure 1 , Figure 2The utility model discloses an embodiment shown, including feeding glove box 1, push plate furnace 2 and discharge glove box 3, be equipped with first sagger transport channel 4 in push plate furnace 2, the feeding end sealed fixed communication of feeding glove box 1 with first sagger transport channel 4, the discharge end sealed fixed communication of discharge glove box 3 with first sagger transport channel 4, the feeding end of first sagger transport channel 4 is equipped with feeding plug-in plate valve 5, and the discharge end of first sagger transport channel 4 is equipped with discharge plug-in plate valve 6, be equipped with the roller way 8 for conveying sagger 7 along its length direction in first sagger transport channel 4, be equipped with air inlet 9 on the lateral wall of the feeding end of first sagger transport channel 4, and the air inlet 9 is connected with inert atmosphere gas source and sintering auxiliary input source, and be equipped with air outlet 10 on the lateral wall of the discharge end of first sagger transport channel 4, and the lateral wall of the discharge end of first sagger transport channel 4 is communicated with multiple condensation collectors 11.

[0032] The push plate furnace 2 is provided with a heating mechanism for segmental heating inside the first sagger transport channel 4, and in specific operation, multi-temperature zone segmental sintering is adopted: the temperature of the first temperature zone is preferably 100-200 DEG C, the holding time is preferably 1-5h; the temperature of the second temperature zone is preferably 200-400 DEG C, the holding time is preferably 1-5h; the temperature of the third temperature zone is preferably 400-600 DEG C, the holding time is preferably 5-15h; the temperature of the fourth temperature zone is preferably 200-400 DEG C, and the holding time is preferably 2-20h.

[0033] The inert atmosphere introduced is preferably argon or nitrogen, and the gas flow is preferably 0.1-10m 3 / h, preferably mixed with sintering auxiliary in the sintering atmosphere at a proportion of 0.1-50%mol.

[0034] In the embodiment of the utility model, the input end of the condensation collector 11 is communicated with the lateral wall of the discharge end of the first sagger transport channel 4, the output end of the condensation collector 11 is connected with the input end of the sulfur-containing tail gas absorption device 12 through the exhaust pipe 18, and the output end of the sulfur-containing tail gas absorption device 12 is connected with the hydrogen sulfide detector 13. The sulfur-containing tail gas absorption device 12 is arranged to absorb the sulfur-containing volatile matter that fails to condense, solve the personnel safety and environmental protection problems, the hydrogen sulfide detector 13 is arranged to monitor the hydrogen sulfide gas in the tail gas purified through the sulfur-containing tail gas absorption device 12 in real time, and avoid the external discharge of the hydrogen sulfide gas.

[0035] The first sagger transport channel 4 is provided with a water-oxygen detection probe 14 for detecting the water-oxygen concentration of the feeding end, a pressure sensor 15 for detecting the internal pressure, a plurality of temperature detection mechanisms for detecting the temperature of each temperature zone, and the push plate furnace 2 is externally provided with a control and feedback system 17 connected with the water-oxygen detection probe 14, the pressure sensor 15, the temperature detection mechanism and the hydrogen sulfide detector 13 to receive the detection signals in real time.

[0036] In order to realize continuous sintering and strict atmosphere control in the whole process, and avoid the material from contacting air during feeding and discharging, the push plate furnace 2 is connected with the feeding glove box 1 and the discharging glove box 3 (the glove box is a laboratory equipment that fills high-purity inert gas into the box body and circulates to filter out active substances, also known as a vacuum glove box, an inert gas protection box, etc.), the furnace chamber can be vacuumized, and an inert atmosphere protection sagger 7 conveying channel is provided to ensure that the whole process related to sintering is carried out in an environment with a water / oxygen concentration of less than 5 ppm.

[0037] Due to the corrosive volatiles generated by sulfides during high-temperature sintering, the material of the key components in the furnace chamber needs to be made of corrosion-resistant material.

[0038] The temperature detection mechanism adopts a S-type thermocouple made of platinum-rhodium alloy, or a K-type thermocouple with a ceramic layer on the surface to prevent temperature measurement inaccuracy caused by corrosion.

[0039] The heating mechanism includes an electric heating assembly and a graphite rod, the graphite rod is arranged in the first sagger transport channel 4, and the electric heating assembly is electrically connected with the graphite rod, or the heating mechanism includes an alloy heating wire, the alloy heating wire is arranged in the first sagger transport channel 4, and a graphite shell layer or a quartz sleeve is arranged on the alloy heating wire. The atmosphere containing corrosive volatiles will not cause corrosion to the graphite rod, or the quartz sleeve is used to protect the general alloy heating wire, or the graphite shell layer is used to isolate the alloy heating wire from the atmosphere containing corrosive volatiles, to prevent uneven temperature field caused by corrosion of the heating component and reduce the cost of consumables.

[0040] Due to the large amount of volatiles and the tendency to re-condense into solids at the cold end, it is necessary to condense and collect them during sintering. A plurality of condensers 11 are arranged at the discharging end to prevent the exhaust pipe 18 from being blocked, causing abnormal rise of furnace pressure, and solve the problem of production safety.

[0041] In the preferred embodiment of the utility model, the push plate furnace 2 is internally provided with a second saggar conveying channel 19 horizontally and parallelly arranged with the first saggar conveying channel 4, both ends of the second saggar conveying channel 19 are respectively communicated with the feeding glove box 1 and the discharging glove box 3, the second saggar conveying channel 19 is internally provided with a conveying mechanism for conveying the saggar 7, the saggar 7 with materials is conveyed from the feeding glove box 1 to the discharging glove box 3 through the first saggar conveying channel 4, after the materials are taken out from the discharging glove box 3, the empty saggar 7 is put into the second saggar conveying channel 19 and is conveyed to the feeding glove box 1 through the conveying mechanism in the second saggar conveying channel 19, so that the saggar 7 is reused.

[0042] In an embodiment of the utility model, the specific process steps of sintering sulfide solid electrolyte by using the above equipment are as follows:

[0043] 1, the sintering temperature is set to 600 DEG C, and the air and moisture adsorbed in the furnace interior are removed through the mode of repeatedly vacuumizing / letting inert atmosphere pass, until the water and oxygen content of the gas outlet end is less than 5ppm;

[0044] 2, in the feeding glove box 1, the mixed precursor powder is filled into the graphite material saggar 7, and the filling depth is 5cm;

[0045] 3, the graphite material saggar 7 filled with reaction materials is pushed into the furnace according to the sintering temperature program, and the sintering temperature program is set as follows: 120 DEG C * 1h (referring to sintering at 120 DEG C for 1h), 300 DEG C * 1h, 500 DEG C * 10h, 200 DEG C * 5h, and then natural cooling, nitrogen and sintering aids are continuously introduced into the furnace during the whole process, the proportion of sintering aids in the atmosphere is 5% mol, the gas flow is 2m 3 / h, and the furnace maintains normal pressure throughout the process; after cooling, the sulfide solid electrolyte material is obtained.

[0046] 4, during the sintering process, the condensation plug-in valve 16 is closed every 2 hours, the condensation collector 11 is taken down, the internal condensed sulfide is cleaned, and then the condensation collector 11 is reinstalled, the condensation plug-in valve 16 is opened, and the plurality of condensers are sequentially operated.

[0047] 5, after cooling, the discharging plug-in valve 6 is opened, the saggar 7 filled with sulfide solid electrolyte material is taken out from the first saggar conveying channel 4, then the sulfide solid electrolyte material in the saggar 7 is taken out, the empty saggar 7 is put into the second saggar conveying channel 19, and is conveyed to the feeding glove box 1 through the conveying mechanism in the second saggar conveying channel 19, so that the saggar 7 is reused.

[0048] The sulfide solid electrolyte continuous sintering device can realize continuous sintering of sulfide solid electrolyte, significantly improve product quality, preparation efficiency and production safety, reduce maintenance cost and improve batch consistency.

[0049] In the description of the utility model, it is understood that the orientation or position relation indicated by the terms "center", "length", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "inner", "outer", "peripheral side", "circumferential direction" and the like is based on the orientation or position relation shown in the drawings, and is only for the convenience of describing the utility model and simplifying the description, and does not indicate or imply that the system or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the utility model.

[0050] In the description of the utility model, the meaning of "a plurality of" is at least two, for example, two, three and the like, unless otherwise explicitly specified and limited.

[0051] In the utility model, unless otherwise explicitly specified and limited, the terms "mounting", "connection", "connection", "fixing" and the like should be understood in a broad sense, for example, can be fixedly connected, or can be detachably connected, or can be integrated; can be mechanically connected, or can be electrically connected; can be directly connected, or can be indirectly connected through an intermediate medium; can be the communication or interaction relationship between two elements, unless otherwise explicitly limited. For ordinary skilled in the art, the specific meaning of the above terms in the utility model can be understood according to the specific circumstances.

[0052] In the description of the specification, the description of the terms "one embodiment", "some embodiments", "example", "specific example" or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the utility model. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine the different embodiments or examples described in the specification and the features of different embodiments or examples without contradiction.

[0053] The above only describes the preferred embodiment of the utility model, and does not limit the utility model, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the utility model should be included in the protection scope of the utility model.

Claims

1. A sintering apparatus for preparing solid electrolytes, characterized in that, The system includes a feeding glove box (1), a pusher furnace (2), and a discharging glove box (3). The pusher furnace (2) is equipped with a first sagger transport channel (4). The feeding glove box (1) is sealed and connected to the feeding end of the first sagger transport channel (4), and the discharging glove box (3) is sealed and connected to the discharging end of the first sagger transport channel (4). The feeding end of the first sagger transport channel (4) is equipped with a feeding gate valve (5), and the discharging end of the first sagger transport channel (4) is equipped with a discharging gate valve (6). The first sagger... The transport channel (4) is provided with a roller conveyor (8) extending along its length for transporting the sagger (7). The feed end of the first sagger transport channel (4) is provided with an air inlet (9), which is connected to an inert atmosphere source. The discharge end of the first sagger transport channel (4) is provided with an air outlet (10). The discharge end of the first sagger transport channel (4) is connected to multiple condensers (11). The pusher furnace (2) is provided with a heating mechanism for segmented heating of the interior of the first sagger transport channel (4).

2. The sintering equipment for preparing solid electrolytes according to claim 1, characterized in that, The input end of the condenser (11) is connected to the side wall of the discharge end of the first sagger transport channel (4), and the output end of the condenser (11) is connected to the input end of the sulfur-containing tail gas absorption device (12) through the exhaust pipe (18).

3. The sintering equipment for preparing solid electrolytes according to claim 2, characterized in that, The output end of the sulfur-containing tail gas absorption device (12) is connected to a hydrogen sulfide detector (13).

4. The sintering equipment for preparing solid electrolytes according to claim 1, characterized in that, The first sagger transport channel (4) is equipped with a water oxygen detection probe (14) for detecting the water oxygen concentration at its feed end.

5. The sintering apparatus for preparing solid electrolytes according to claim 1, characterized in that, The first sagger transport channel (4) is equipped with a pressure sensor (15) for detecting its internal pressure.

6. A sintering apparatus for preparing solid electrolytes according to claim 1, characterized in that, The first sagger transport channel (4) is equipped with multiple temperature detection mechanisms for detecting the temperature of each temperature zone.

7. A sintering apparatus for preparing solid electrolytes according to claim 6, characterized in that, The temperature detection mechanism uses an S-type thermocouple made of platinum-rhodium alloy or a K-type thermocouple with a ceramic layer on its surface.

8. A sintering apparatus for preparing solid electrolytes according to any one of claims 1 to 7, characterized in that, The heating mechanism includes an electric heating component and a graphite rod. The graphite rod is disposed in the first sagger transport channel (4), and the electric heating component is electrically connected to the graphite rod.

9. A sintering apparatus for preparing solid electrolytes according to any one of claims 1 to 7, characterized in that, The heating mechanism includes an alloy heating wire, which is located in the first sagger transport channel (4). The alloy heating wire is covered with a graphite shell or a quartz sleeve.

10. A sintering apparatus for preparing solid electrolytes according to any one of claims 1 to 7, characterized in that, The air inlet (9) is connected to the sintering aid input source.

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