CN112683058A - Vacuum rapid quenching equipment for preparing solid electrolyte material - Google Patents
Vacuum rapid quenching equipment for preparing solid electrolyte material Download PDFInfo
- Publication number
- CN112683058A CN112683058A CN202011566846.3A CN202011566846A CN112683058A CN 112683058 A CN112683058 A CN 112683058A CN 202011566846 A CN202011566846 A CN 202011566846A CN 112683058 A CN112683058 A CN 112683058A
- Authority
- CN
- China
- Prior art keywords
- rapid quenching
- chamber
- solid electrolyte
- smelting
- feeding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Crucibles And Fluidized-Bed Furnaces (AREA)
Abstract
A vacuum rapid quenching apparatus for producing a solid electrolyte material, comprising: the equipment body comprises a smelting chamber, a rapid quenching chamber and a tundish; an induction smelting device is arranged in the smelting chamber, and the induction smelting device can be driven by a turnover mechanism to turn over under the driving of a driving mechanism so as to pour the molten liquid into a tundish; a quick quenching roller device is arranged in the quick quenching chamber and is correspondingly arranged below the discharge hole of the tundish; the vacuum rapid quenching equipment further comprises a protective feeding device and a material receiving device, wherein the protective feeding device is communicated with the smelting chamber through a feeding channel, the material receiving device is communicated with the rapid quenching chamber through a discharging channel, and the material receiving device receives and stores the solid electrolyte material formed by rapid quenching of the rapid quenching roller device. According to the invention, the linear velocity of the roller surface of the rapid quenching roller device is controlled within the range of 1-100 m/s, and the circular runout of the roller surface is controlled within 3 mu m, so that the solid electrolyte material with small particle size and concentrated particle size distribution is obtained, and the industrial mass production of the solid electrolyte material can be realized.
Description
Technical Field
The invention relates to the technical field of solid electrolyte material preparation, in particular to vacuum rapid quenching equipment for preparing a solid electrolyte material.
Technical Field
With the lapse of time, the traditional power battery system (lithium ion battery based on liquid electrolyte) will be difficult to meet the energy density requirement after 10 years, and as is well known, the power battery directly corresponds to the cost performance of new energy vehicle products, and the energy density is a key index of the power battery. The solid-state battery has the characteristics of high energy density, good safety, strong cyclicity, wide application range and the like, so the solid-state battery becomes a necessary path, the solid-state battery adopts non-flammable solid electrolyte to replace flammable organic liquid electrolyte, the safety of a battery system can be greatly improved, meanwhile, the high-energy anode and cathode can be better adapted, the weight of the system is reduced, and the synchronous improvement of the energy density is realized. The all-solid-state battery is one of the emerging technical directions which are acknowledged by the industry at present and are expected to break through the technical bottleneck of electrochemical energy storage and meet the development requirements in the future.
US patents CN107004893A, US20120040233a1, etc. of Sakti3 limited, propose to use multi-chamber coating technology to deposit corresponding film layers by physical vapor deposition method using vacuum chambers connected in series, and to repeat many times of stacking of the corresponding film layers by cyclic and repeated deposition to obtain high energy density, which is difficult to realize large-scale, low-cost, and high-efficiency production by using thin film deposition process similar to that for producing flat panel displays and photovoltaic solar cells.
Patents CN108232290A and CN108232308A of japan toyota automotive co, etc., propose to micronize a solid electrolyte material by ball milling, and to treat the mixed starting material by high energy ball milling, and obtain the solid electrolyte after ball milling for a certain time.
Therefore, it is desirable to provide a production apparatus capable of solving the problem that the solid electrolyte cannot be produced safely and efficiently in large quantities.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the vacuum rapid quenching equipment for preparing the solid electrolyte material is high in efficiency and suitable for large-scale mass production.
In order to solve the technical problems, the invention adopts the following technical scheme:
the vacuum rapid quenching equipment for preparing the solid electrolyte material mainly comprises:
the equipment body comprises a smelting chamber and a quick quenching chamber, and a tundish is arranged between the smelting chamber and the quick quenching chamber; the induction smelting device is arranged in the smelting chamber and is provided with a driving mechanism and a turnover mechanism, and the turnover mechanism can be driven by the driving mechanism to turn over so as to pour the molten liquid in the induction smelting device into the tundish; a quick quenching roller device is arranged in the quick quenching chamber and correspondingly arranged below a discharge hole of the tundish;
the vacuum rapid quenching equipment also comprises a protective feeding device and a material receiving device, wherein the protective feeding device is communicated with the smelting chamber through a feeding channel, and the induction smelting device is correspondingly arranged below the discharging end of the feeding channel; the material receiving device is communicated with the rapid quenching chamber through a discharge channel and can receive and store the solid electrolyte material formed by rapid quenching of the rapid quenching roller device.
Further, the air conditioner is provided with a fan,
the rapid quenching roller device mainly comprises two mounting seats and a rotating shaft, wherein two ends of the rotating shaft are respectively erected on the two mounting seats, the rotating shaft is provided with a roller surface, and a cooling water channel is arranged in the rotating shaft.
Preferably, the roller surface of the rapid quenching roller device is made of copper or copper alloy, so that the heat transfer effect is better, rapid cooling can be realized, and the rapid quenching effect is improved.
Further, the air conditioner is provided with a fan,
the equipment is vacuum rapid quenching equipment for industrial preparation of the solid electrolyte material, and in order to adapt to the application, a rapid quenching roller of the equipment needs to keep an extremely low roller surface circular runout index at a high linear speed of a rotating roller, and the technical index can keep a rapid hardening contact surface (roller surface) of the solid electrolyte material stable, so that the produced solid electrolyte material powder particles are uniform and fine, the particle size distribution is concentrated, and the high quality of the solid electrolyte material is ensured.
The linear velocity of the roller surface is controlled to be adjustable within the range of 1-100 m/s, and the circular runout of the roller surface is controlled within 3 mu m at the linear velocity of 1-100 m/s, so that the solid electrolyte material with small particle size and concentrated particle size distribution is obtained.
Further, the air conditioner is provided with a fan,
the tundish has induction heating, temperature control and position adjustment functions, and structurally has an overflow structure or a bottom leakage structure with a nozzle at the bottom.
Specifically, when the tundish is of a bottom leakage type structure with a nozzle at the bottom, the bottom nozzle is arranged in a single row or is in a single long shape.
Preferably, the tundish is made of refractory material.
Further, the air conditioner is provided with a fan,
the induction smelting device is also provided with an induction coil and a crucible, and the induction coil is used for heating the melt in the crucible.
Preferably, the first and second electrodes are formed of a metal,
the induction melting device adopts medium-frequency induction heating, the induction coil is connected with a medium-frequency power supply through an electrode introducing device, and the medium-frequency induction heating is realized by supplying power to the induction coil through the medium-frequency power supply. Preferably, the electrode introducing device is a coaxial electrode, or a water-cooled cable or other structural forms.
Because the induction melting device adopts intermediate frequency induction heating, if the material electromagnetic conductivity is relatively poor, add the graphite inside lining in the crucible, heat the material through heat-conduction, can improve the heating effect.
Furthermore, in order to control the temperature of the molten liquid in the smelting process, the smelting chamber is provided with a temperature measuring device, and the temperature measuring device is used for realizing the rapid temperature measurement of the molten liquid.
Furthermore, in order to control the components of the molten liquid and ensure the quality of the prepared material in the smelting process, the smelting chamber is provided with an online component monitoring system, and the online component monitoring system comprises an online sampling analysis device and a component adjusting device; the online sampling and analyzing device is used for online sampling and analyzing the molten liquid in the induction smelting device during refining; the component adjusting device is used for providing component adjusting materials to be added when the components of the molten liquid have deviation, and adding the component adjusting materials into the molten liquid in the induction smelting device through the protective feeding device for component adjustment.
Further, the inside of the protective feeding device is vacuumized and/or filled with protective gas, and the protective feeding device is used for filling raw materials into the induction melting device under the environment of isolating the external atmosphere and moisture; and a feeding isolation valve is arranged on the feeding channel.
Further, the air conditioner is provided with a fan,
the feeding protection device in the embodiment comprises a feeding chamber and a glove box, wherein a valve is arranged between the feeding chamber and the glove box; the glove box is a glove box with a weighing function, and is provided with a powdery raw material container interface, a granular container interface and/or a block raw material container interface.
The specific feeding process is as follows: raw materials of solid electrolyte are subjected to external mixed briquetting treatment or are directly added into a feeding chamber, then are conveyed into a special glove box with a weighing function, then the glove box is vacuumized and filled with protective gas for treatment, and then the raw materials are protected and are added into a smelting chamber to provide the same vacuum environment, the smelting chamber and the glove box are separated by a valve when secondary feeding is needed, the smelting chamber is still kept in a vacuum state, only the glove box is communicated with the atmosphere, after feeding is completed, the glove box is firstly vacuumized and filled with argon, and after the glove box reaches a certain vacuum degree, the glove box is communicated with the smelting chamber to start to be smelted again, so that rapid feeding is realized.
Preferably, the feeding chamber is a cylindrical structure or a magazine structure formed by combining a plurality of cubes. After primary smelting is finished, secondary feeding is carried out, only solid electrolyte raw materials are required to be added into the feeding chamber, a valve between the feeding chamber and the glove box is opened, the raw materials are made to enter the glove box, the valve between the feeding chamber and the glove box is closed again, then the glove box is vacuumized and filled with protective gas for treatment, the vacuum condition of the glove box is consistent with that of the smelting chamber, a feeding isolation valve of a feeding channel between the glove box and the smelting chamber is opened again, the raw materials enter an induction smelting device along the feeding channel, the secondary exhaust process of the induction smelting chamber is reduced, the exhaust time is greatly shortened, and the production efficiency is obviously improved.
Further, the air conditioner is provided with a fan,
the interior of the material receiving device is also vacuumized and/or filled with protective gas, and the material receiving device is provided with a water cooling system; and a discharge valve is arranged on the discharge channel.
Further, the air conditioner is provided with a fan,
oxygen and moisture monitoring instruments are arranged in the protective feeding device, the smelting chamber, the rapid quenching chamber and the material receiving device.
Further, the air conditioner is provided with a fan,
the vacuum rapid quenching equipment further comprises a vacuum pumping system, an air charging and discharging system, a water cooling system and a control system, wherein the vacuum pumping system, the air charging and discharging system and the water cooling system are respectively in signal connection with the control system; and are respectively communicated with the areas needing vacuumizing, air charging and discharging and water cooling.
Because the solid electrolyte material and the raw materials thereof are very sensitive to atmosphere and moisture, even trace amount of atmosphere or moisture contact can cause the solid electrolyte material and the raw materials thereof to react to cause danger or influence the material quality, therefore, the raw material feeding, smelting and material discharging processes of the equipment are required to be carried out in the environment isolating the outside atmosphere and moisture.
In order to ensure production safety and product quality, oxygen and moisture monitoring instruments are arranged in the protective feeding device, the smelting chamber, the rapid quenching chamber and the material receiving device in the equipment. When the concentration of the moisture or the oxygen in the environment exceeds the set standard, an alarm signal is sent out to remind an operator to stop the corresponding process. Specifically, the oxygen and moisture monitoring instrument that set up in the protection feed arrangement in the feeding process, moisture or oxygen concentration in the feeding environment surpass the set standard and can send alarm signal, remind the operator to stop the feeding process. An oxygen and moisture monitoring instrument arranged in the smelting chamber can send out an alarm signal to remind an operator to stop a smelting process when moisture or oxygen concentration in a smelting environment exceeds a set standard in the smelting process. In the discharging process, when the moisture or oxygen concentration in the environment exceeds the set standard, an alarm signal is sent out to remind an operator to stop the discharging process.
Meanwhile, a vacuum pumping system and an air charging and discharging system are arranged, so that the corresponding working process (including feeding, smelting, quick quenching and discharging) can be carried out in a relatively oxygen-free and water-free vacuum environment. The gas charging and discharging system is used for charging and discharging protective gas to and from the equipment, the protective gas is nitrogen, argon and the like, preferably argon, the gas charging and discharging system can realize automatic control of the argon charging process, can charge argon to a melting chamber and a rapid quenching chamber to set pressure, and the gas discharging adopts two modes of automation and manual operation.
The water cooling system is used for cooling equipment needing cooling, such as a power supply, a furnace shell, an induction melting device, accessory equipment and the like, and ensures safe and reliable operation of the vacuum rapid quenching equipment. The water return paths of the induction melting device, the quick quenching roller device and the tundish are provided with flow indicators, and when the water supply fails, the flow indicators display the water flow conditions.
Further, the air conditioner is provided with a fan,
because the solid electrolyte material can generate and release harmful gas substances such as hydrogen sulfide, sulfur dioxide and the like in the smelting preparation process, the equipment is provided with a filtering system in order to ensure the safety of the equipment and the personnel. The filtering system is arranged at the upstream of the vacuum quick quenching equipment for exhausting gas to the outside. In particular, the amount of the solvent to be used,
a filtering system is arranged between the vacuumizing system and the equipment body; a filtering system is also arranged between the air charging and discharging system and the equipment body; the filtering system mainly comprises a shell, a filter screen and an absorbing material.
The filter screen is used for removing a part of solid pollutants, and the absorption material is used for filtering and removing toxic gases possibly contained in the discharged gas in the vacuum rapid quenching equipment by means of physical absorption and/or chemical neutralization. The absorbing material is one or more of a solvent gas absorbing material and a solid gas absorbing material.
Further, the air conditioner is provided with a fan,
the melting chamber and the quick quenching chamber are provided with safety valves for pressure relief protection when the pressure in the furnace exceeds a safety limit value, and the maximum melting temperature of the melting chamber can reach 1700 ℃.
All the valves in the equipment are driven in a pneumatic mode and are interlocked with the system, so that all the valves are automatically and quickly closed when power is cut off, the vacuum state of the smelting chamber is ensured, bad and waste materials caused by sudden power failure are prevented, and the production efficiency is improved.
Furthermore, a smelting observation window and a casting observation window are arranged on the vacuum rapid quenching equipment, so that an operator can conveniently observe and operate; the observation window adopts a structure capable of being cleaned repeatedly and is provided with a heat insulation baffle plate to prevent the temperature of the lens from being overhigh.
Furthermore, an operating platform is arranged on a furnace shell of an equipment body of the vacuum rapid quenching equipment and used for operators to work, and an operating panel is arranged on the operating platform and used for smelting rapid quenching operation.
In the equipment, the tilting of the induction smelting device, the lifting action of the furnace upper cover and other actions of the equipment are driven by hydraulic drive. The electric control system is provided with a touch screen, a PLC control system, a vacuum gauge, a casting controller and a recorder on an electric control cabinet, can realize real-time operation and display of process pictures, and has the functions of historical record and sound and light alarm of various safety protections (vacuum abnormity, water pressure, water temperature, water flow abnormity, valve abnormity, limit switch abnormity, pump abnormity, hydraulic system abnormity, automatic casting condition abnormity, low air source pressure, high moisture or oxygen content and the like).
The invention has the following beneficial effects:
the vacuum rapid quenching equipment provided by the invention can obtain the solid electrolyte material with small particle size and concentrated particle size distribution by simultaneously controlling the linear velocity of the roller surface and the circular runout of the roller surface of the rapid quenching roller device. Furthermore, the vacuum rapid quenching equipment can also be popularized and applied to the preparation of powder for additive manufacturing such as 3D printing and the like, and high-performance metal and alloy ultra-micro powder.
The single-furnace yield of the vacuum rapid quenching equipment provided by the invention can be 50-1000 kg, and can be increased to over 1000kg under the condition of being provided with a large-capacity crucible. Compared with the preparation of solid electrolyte with 5-10 kg magnitude in the prior art, the vacuum rapid quenching equipment provided by the invention can realize the industrial mass production of solid electrolyte materials.
The vacuum rapid quenching equipment provided by the invention has the characteristics of compact structure, simplicity in operation, safety and high efficiency.
Drawings
Fig. 1 is a schematic structural view of embodiment 1 of the vacuum rapid quenching apparatus of the present invention.
Fig. 2 is a schematic structural view of embodiment 2 of the vacuum rapid quenching apparatus of the present invention.
Fig. 3 is a schematic structural diagram of a filtering system of a vacuum rapid quenching apparatus according to an embodiment of the present invention.
Fig. 4 is a schematic structural diagram of a rapid quenching roller device of vacuum rapid quenching equipment according to an embodiment of the invention.
Description of reference numerals: the device comprises a smelting chamber 1, a turnover mechanism 2, an induction smelting device 3, a driving mechanism 4, a temperature measuring device 5, a tundish 6 (6'), a rapid quenching chamber 7, a rapid quenching roller device 8, a control system 9, an air charging and discharging system 10, a filtering system 11, a protective feeding device 12, a vacuum system 13, a water cooling system 14, an intermediate frequency power supply 15, a material receiving device 16, a mounting seat 801, a rotating shaft 802, a shell 1101, a filter screen 1102 and an absorbing material 1103.
Detailed Description
In order to better illustrate the content of the invention, the invention is further verified by the following specific examples. It should be noted that the examples are given for the purpose of describing the invention more directly and are only a part of the present invention, which should not be construed as limiting the invention in any way.
Apparatus example 1
As shown in fig. 1, a vacuum rapid quenching apparatus for preparing a solid electrolyte material is provided, which mainly comprises:
the equipment comprises an equipment body, wherein the equipment body comprises a smelting chamber 1 and a rapid quenching chamber 7, and a tundish 6 is arranged between the smelting chamber 1 and the rapid quenching chamber 7; the smelting chamber 1 and the quick quenching chamber 7 of the embodiment are arranged in a shell, the interior of the shell of the equipment is divided into the smelting chamber 1 and the quick quenching chamber 7, and the tundish 6 is fixedly arranged at the division of the smelting chamber 1 and the quick quenching chamber 7. It can be understood that the smelting chamber and the rapid quenching chamber are not arranged in a shell, and two independent equipment bodies are communicated through the tundish, so that the smelting chamber and the rapid quenching chamber can be realized and also belong to the protection scope of the invention.
An induction smelting device 3 is arranged in the smelting chamber 1, the induction smelting device 3 is provided with a driving mechanism 4 and a turnover mechanism 2, the turnover mechanism in the embodiment is specifically a rotating shaft, and the rotating shaft can be turned over under the driving of the driving mechanism 4 so as to pour the molten liquid in the induction smelting device 3 into a tundish 6;
a rapid quenching roller device 8 is arranged in the rapid quenching chamber 7, and the rapid quenching roller device 8 is correspondingly arranged below the discharge hole of the tundish 6.
The vacuum rapid quenching equipment provided by the invention also comprises a protective feeding device 12 and a material receiving device 16, wherein the protective feeding device 12 is communicated with the smelting chamber 1 through a feeding channel, and the induction smelting device 3 is correspondingly arranged below the discharging end of the feeding channel; the material receiving device 16 is communicated with the rapid quenching chamber 7 through a discharge channel and can receive and store the solid electrolyte material formed by the rapid quenching roller device 8.
The whole equipment works in a closed vacuum state, so that the whole preparation process is relatively oxygen-free and water-free, and the quality of the product is ensured.
As a preferred embodiment, as shown in fig. 3, the rapid quenching roller device 8 in this embodiment mainly comprises two mounting seats 801 and a rotating shaft 802, two ends of the rotating shaft 802 are respectively erected on the two mounting seats 801, the rotating shaft 802 has a roller surface, and a cooling water channel is arranged in the rotating shaft 802 and connected to the water cooling system 28. One end of the rotating shaft is connected with a driving mechanism, the rotating shaft is driven by the driving mechanism to rotate, and the driving mechanism is generally a motor. The roller surface is made of copper or copper alloy, so that the heat transfer effect is better, quick cooling can be realized, and the quick quenching effect is improved.
In order to adapt to the application, the rapid quenching roller device 8 needs to keep an extremely low roller surface circular runout index at a high linear speed of a rotating roller, and the technical index can keep a rapid hardening contact surface (roller surface) of the solid electrolyte material stable, so that the produced solid electrolyte material powder particles are uniform and fine, the particle size distribution is concentrated, and the high quality of the solid electrolyte material is ensured. In the specific application process, the linear velocity of the roller surface is adjustable within the range of 1-100 m/s, and the circular runout of the roller surface is controlled within 3 mu m at the linear velocity of 1-100 m/s, so that the solid electrolyte material with small particle size and concentrated particle size distribution is obtained.
In the preferred embodiment, the tundish 6 has induction heating, temperature control and position adjustment functions, in the embodiment, the tundish 6 adopts a bottom leakage type structure with nozzles at the bottom, the nozzles at the bottom are arranged in a single row or are in a single long shape, and the melt poured into the tundish 6 can be rapidly sprayed onto the roller surface of the rapid quenching roller device 8 through the nozzles at the bottom and rapidly condensed into solid electrolyte materials with different particle sizes under the water cooling effect. Preferably, the tundish is made of refractory material.
As a preferred embodiment, the induction melting device 3 is further provided with an induction coil and a crucible; the induction coil is used for heating the melt in the crucible. The induction melting device adopts intermediate frequency induction heating, the induction coil is connected with the intermediate frequency power supply 15 through the electrode introducing device, and the induction coil is supplied with power through the intermediate frequency power supply, so that the intermediate frequency induction heating is realized. Preferably, the electrode introducing device is a coaxial electrode, or a water-cooled cable or other structural forms. Because the induction melting device adopts intermediate frequency induction heating, if the material electromagnetic conductivity is relatively poor, add the graphite inside lining in the crucible, heat the material through heat-conduction, can improve the heating effect.
In order to control the temperature of the melt in the smelting process, the smelting chamber 1 is provided with a temperature measuring device 5 as a preferred embodiment, and the temperature measuring device 5 is used for realizing the rapid temperature measurement of the melt.
As a preferred embodiment, in order to control the components of the melt and ensure the quality of the prepared material in the smelting process, the smelting chamber 1 is provided with an online component monitoring system, and the online component monitoring system comprises an online sampling analysis device and a component adjusting device; the online sampling and analyzing device is used for online sampling and analyzing the melt in the induction smelting device 3 during refining; the component adjusting device is used for providing component adjusting materials to be added when the components of the molten liquid have deviation, and adding the component adjusting materials into the molten liquid in the induction melting device 3 through the protective feeding device 12 for component adjustment.
As a preferred embodiment, the inside of the protective feeding device 12 is vacuumized by the vacuumizing system 13 and filled with protective gas by the inflation and deflation system 10, and the protective feeding device 12 is used for filling raw materials into the induction melting device 3 in an environment isolated from the external atmosphere and moisture; and a feeding isolation valve is arranged on the feeding channel.
As a preferred embodiment, the feeding protection device 12 in this embodiment includes a feeding chamber and a glove box, and a valve is disposed between the feeding chamber and the glove box; the glove box is a glove box with a weighing function, and is provided with a powdery raw material container interface, a granular container interface and/or a block raw material container interface.
The specific feeding process is as follows: raw materials of solid electrolyte are subjected to external mixed briquetting treatment or are directly added into a feeding chamber, then are conveyed into a special glove box with a weighing function, then the glove box is vacuumized and filled with protective gas for treatment, and then the raw materials are protected and are added into a smelting chamber to provide the same vacuum environment, the smelting chamber and the glove box are separated by a valve when secondary feeding is needed, the smelting chamber is still kept in a vacuum state, only the glove box is communicated with the atmosphere, after feeding is completed, the glove box is firstly vacuumized and filled with argon, and after the glove box reaches a certain vacuum degree, the glove box is communicated with the smelting chamber to start to be smelted again, so that rapid feeding is realized.
Preferably, the feeding chamber is a cylindrical structure or a magazine structure formed by combining a plurality of cubes. After primary smelting is finished, secondary feeding is carried out, only solid electrolyte raw materials are required to be added into the feeding chamber, a valve between the feeding chamber and the glove box is opened, the raw materials are made to enter the glove box, the valve between the feeding chamber and the glove box is closed again, then the glove box is vacuumized and filled with protective gas for treatment, the vacuum condition of the glove box is consistent with that of the smelting chamber, a feeding isolation valve of a feeding channel between the glove box and the smelting chamber is opened again, the raw materials enter an induction smelting device along the feeding channel, the secondary exhaust process of the induction smelting chamber is reduced, the exhaust time is greatly shortened, and the production efficiency is obviously improved.
As a preferred embodiment, the inside of the material receiving device 16 is also vacuumized by the vacuum-pumping system 13 and filled with protective gas by the air charging and discharging system 10, and the material receiving device 16 is provided with a water cooling structure and connected with the water cooling system 14; and a discharge valve is arranged on the discharge channel. In this embodiment, the material receiving device 16 is specifically a material receiving tank.
As a preferred embodiment, oxygen and moisture monitoring instruments are arranged in the protective feeding device 12, the smelting chamber 1, the rapid quenching chamber 7 and the material receiving device 16. When the water or oxygen concentration in the environment exceeds the set standard, an alarm signal is sent out to remind an operator to stop the corresponding process, and the preparation of the solid electrolyte material is ensured to be carried out in a relatively oxygen-free and water-free environment so as to avoid danger or influence on the quality of the material.
As a preferred embodiment, the vacuum rapid quenching equipment further comprises a vacuum pumping system 13, an air charging and discharging system 10, a water cooling system 14, a control system 9, a vacuum pumping system 13, an air charging and discharging system 10, and a water cooling system 14, which are respectively in signal connection with the control system 9; and are respectively communicated with the areas needing vacuumizing, air charging and discharging and water cooling. The gas charging and discharging system 10 is used for charging and discharging protective gas for equipment and discharging gas after preparation, the protective gas is nitrogen, argon and the like, preferably argon, the gas charging and discharging system can realize automatic control of the argon charging process, can charge argon into the smelting chamber and the rapid quenching chamber to set pressure, and the gas discharging adopts two modes of automation and manual operation. The water cooling system 14 is used for cooling equipment needing cooling, such as a power supply, a furnace shell, the induction melting device 3 and accessory equipment, and ensures safe and reliable operation of the vacuum rapid quenching equipment. The water return paths of the induction melting device 3, the quick quenching roller device 8 and the tundish 6 are provided with flow indicators, and when the water supply fails, the condition of the water flow is displayed.
As the solid electrolyte material can generate and release toxic gas substances such as hydrogen sulfide, sulfur dioxide and the like in the smelting preparation process, the equipment is provided with a filtering system 11 in order to ensure the equipment and personal safety. The filtering system 11 is arranged at the upstream of the vacuum rapid quenching equipment for exhausting gas to the outside. As a preferred embodiment, a filtering system 11 is arranged between the vacuum-pumping system 13 and the equipment body; a filtering system 11 is also arranged between the inflation and deflation system 10 and the equipment body. As shown in fig. 4, the filter system 11 mainly includes a housing 1101, a filter screen 1102, and an absorbent material 1103. The filter screen 1102 is used for removing a part of solid pollutants, and the absorption material 1103 is used for filtering and removing toxic gases possibly contained in the exhaust gas in the vacuum rapid quenching equipment by means of physical adsorption and/or chemical neutralization. Preferably, the absorbing material 1103 is one or more of a solvent-based gas absorbing material, a solid gas absorbing material.
As a preferred embodiment, the smelting chamber 1 and the quick quenching chamber 7 are also provided with safety valves for pressure relief protection when the pressure in the smelting chamber exceeds a safety limit value, and the maximum smelting temperature of the smelting chamber can reach 1700 ℃. The action of all valves in the equipment is driven in a pneumatic mode and is interlocked with a system, so that all valves are automatically and quickly closed when power is cut off, the vacuum state of a smelting chamber is ensured, bad and waste materials caused by sudden power failure are prevented, and the production efficiency is improved.
As a preferred embodiment, the vacuum rapid quenching equipment is also provided with a smelting observation window and a casting observation window, so that the operation of operators can be conveniently observed; the observation window adopts a structure capable of being cleaned repeatedly and is provided with a heat insulation baffle plate to prevent the temperature of the lens from being overhigh.
As a preferred embodiment, the furnace shell of the equipment body of the vacuum rapid quenching equipment is also provided with an operating platform for operators to work, and the platform is provided with an operating panel for smelting rapid quenching operation.
In the equipment, the tilting of the induction smelting device, the lifting action of the furnace upper cover and other actions of the equipment are driven by hydraulic drive. The electric control system is provided with a touch screen, a PLC control system, a vacuum gauge, a casting controller and a recorder on an electric control cabinet, can realize real-time operation and display of process pictures, and has the functions of historical record and sound and light alarm of various safety protections (vacuum abnormity, water pressure, water temperature, water flow abnormity, valve abnormity, limit switch abnormity, pump abnormity, hydraulic system abnormity, automatic casting condition abnormity, low air source pressure, high moisture or oxygen content and the like).
The specific working process of the equipment is as follows:
firstly, powdery, granular or blocky raw materials can be directly loaded into a glove box through a corresponding interface, or the powdery or granular raw materials are firstly pressed into blocky raw materials and then added into a feeding chamber, then the blocky raw materials are conveyed into a special glove box with a weighing function, solid electrolyte raw materials with certain mass are weighed and then added into a crucible through a feeding channel. The protective feeding device 12 (including the glove box and the feeding chamber) is provided with an oxygen and moisture monitoring instrument, and when the moisture or oxygen concentration in the feeding environment exceeds a set standard, an alarm signal is sent out to remind an operator to stop the feeding process, so as to avoid the material from generating harmful reactions with the oxygen or water, for example, the solid electrolyte raw material and the oxygen or water can generate toxic and harmful sulfur dioxide and hydrogen sulfide gas. After the feeding is finished, the feeding isolation valve is closed, and the vacuumizing is started, so that the background vacuum degree in the equipment is higher than 6.7 multiplied by 10-1Pa, and then starting the intermediate frequency power supply 16 to heat the furnace burden. In order to prevent the material from volatilizing and losing, protective gas with certain pressure needs to be filled in the smelting process. The heating of melting process is intermediate frequency induction heating, if material electromagnetic conductivity is relatively poor, adds the graphite inside lining in the crucible, heats the material through heat-conduction. An oxygen and moisture monitoring instrument is also arranged in the smelting chamber 1, and in the smelting process, when the moisture or oxygen concentration in the smelting environment exceeds the set standard, an alarm signal is sent out to remind an operator to stop the smelting process. When the materials in the crucible are completely meltedThereafter, the refining process is started. During refining, the molten liquid needs to be subjected to contact temperature measurement, the molten liquid state is timely mastered, and whether the molten liquid temperature reaches the proper pouring temperature or not is known. In addition, during refining, the melt in the crucible needs to be sampled and analyzed on line through an online sampling and analyzing device of an online component monitoring system, when the components of the melt have deviations, a component adjusting material needing to be added is provided through a component adjusting device of the online component monitoring system, and the component adjusting material is added into the melt in the crucible through a protective feeding device to adjust the components. When the temperature and the components of the melt meet the requirements, the process of pouring and quick quenching is started. The melt in the crucible is poured into the tundish 6 at the lower part by the turning and tilting action of the rotating shaft. The tundish 6 has the function of heating and temperature control, so that the melt injected into the tundish can keep a certain temperature, the melt is sprayed onto the roll surface of the rapid quenching roll device 8 rotating at a high speed through the tundish 6, the melt is rapidly condensed into solid electrolyte materials with different particle sizes by simultaneously controlling the linear velocity of the roll surface and the circular runout of the roll surface, the solid electrolyte materials in an amorphous state are received and stored by the material receiving tank after falling, and the material receiving tank is provided with water cooling, vacuumized and filled with protective gas. In order to ensure the safety of equipment and human bodies, at the upstream of the gas discharged to the outside by the vacuum rapid quenching equipment, part of solid pollutants are removed through a filter screen 1102 of the filter system 11, and then the toxic gas possibly contained in the gas discharged in the vacuum rapid quenching equipment is filtered and removed through an absorption material arranged in the filter system 11 in a physical adsorption and/or chemical neutralization mode.
Apparatus example 2
As shown in fig. 2, this example provides another vacuum rapid quenching apparatus for producing a solid electrolyte material, which is different from example 1 in that:
the tundish 6 'adopts an overflow structure, namely, the melt injected into the tundish 6' overflows in an overflow mode and falls onto the roll surface of the rapid quenching roll device 8;
melting chamber 1 and rapid quenching chamber 7 are also provided in one housing, but different from embodiment 1 in that melting chamber 1 and rapid quenching chamber 7 are not partitioned but are in a space, and tundish 6' is provided between melting chamber 1 and rapid quenching chamber 7.
Preparation example 1:
the vacuum rapid quenching device provided in the above example 1 or 2 is used to prepare a solid electrolyte material, and the detailed working process is not repeated here. Specifically, a sulfide solid electrolyte raw material is made to have a molar ratio of Li2S:P2S5The method comprises the steps of weighing LiBr and LiI in a mode of 56.25:18.75:15:10, weighing the raw materials with the total weight of 1000kg, directly loading the raw materials in a protective feeding device through corresponding interfaces, or firstly pressing the raw materials in powder, granules or blocks into the block raw materials, adding the block raw materials into the protective feeding device, conveying the block raw materials into a special glove box with the weighing function, weighing the raw materials of the solid electrolyte with the total weight of 1000kg, and then adding the raw materials into a crucible through a feeding channel. Controlling the heating temperature of the crucible, carrying out contact temperature measurement on the melt after the materials in the crucible are completely melted, grasping the state of the melt in time, monitoring and adjusting the components of the melt, and when the temperature and the components of the melt meet the requirements, overturning and dumping the melt in the crucible through a rotating shaft to inject the melt into a tundish at the lower part. The melt is sprayed onto the surface of a fast quenching roller rotating at a high speed through a tundish, and is rapidly condensed into solid electrolyte materials with different particle sizes by controlling the linear speed of the roller surface, the linear speed of the roller surface is set to be 60m/s, the circular runout of the roller surface at the linear speed of 60m/s is controlled within 3 mu m, the solid electrolyte particles in an amorphous state are received and stored by a material receiving tank after falling, the material receiving tank is provided with water cooling, and the material receiving tank is vacuumized and filled with protective gas. And finally, exhausting gas after preparation.
The whole preparation process of this example is obtained from the initial vacuum environment, the addition of the solid electrolyte raw materials to the completion of the preparation of the final solid electrolyte, the time taken is about 3 hours, and mass production can be realized. After particle size testing, the average particle size of the solid electrolyte material prepared by the equipment is about 3 μm, the particle distribution proportion of the particle size in the range of 2-5 μm accounts for about 90%, and the particle size distribution is more concentrated.
Preparation example 2:
the difference from preparation example 1 is that:
in this preparation example, the total weight of the raw materials of the sulfide solid electrolyte is 500kg, and the molar ratio of each component in the raw materials is Li2S:P2S5The specific operation process refers to the specific working process of the equipment.
In the preparation process, the linear velocity of the roll surface of the rapid quenching roll device 8 is controlled to be 35m/s, the circular runout of the roll surface under the linear velocity of 35m/s is controlled within 3 mu m, and the amorphous solid electrolyte particles are received and stored by a material receiving tank after falling. The exhaust gas after preparation is likewise carried out last.
The whole preparation process of preparation example 2 was obtained from the initial vacuum environment, and the addition of the solid electrolyte raw materials to the completion of the preparation of the final solid electrolyte took about 2 hours, and mass production was also possible. After particle size testing, the solid electrolyte material prepared by the equipment has an average particle size of about 5 μm, the particle distribution proportion of the particles with the particle size in the range of 3-7 μm accounts for about 85%, and the particle size distribution is more concentrated.
Comparative example:
the sulfide solid electrolyte material is prepared by adopting the conventional common ball milling process route.
First, a solid electrolyte is synthesized by mainly converting a solid electrolyte raw material into Li in a molar ratio2S:P2S5LiBr LiI 56.25:18.75:15:10, and the weighed electrolyte raw materials were put into a container of a planetary ball mill (45ml, ZrO) together with tridecane2Preparation), and ZrO of 5mm diameter was added2The ball is dropped into the container, and the container is completely sealed. Mechanical milling was performed at 310rpm for 21 hours, whereby the electrolyte raw material was amorphized to synthesize a sulfide solid electrolyte material 75(0.75 Li)2S·0.25P2S5) 15LiBr 10 LiI. Then, the sulfide solid electrolyte material 85g, dehydrated heptane 130g and dehydrated water recovered from the container after the synthesis step were subjected to microparticulation treatment90g of n-butyl ether and 450g of ZrO2 grinding medium (particle size) were charged with ZrO2In can making, the can was completely sealed (Ar atmosphere). The pot was mounted on a planetary ball mill, wet mechanical milling was performed at 200rpm for 21 hours, thereby micronizing the sulfide solid electrolyte material, and finally, drying and heating treatment were performed to prepare a sulfide electrolyte, which took about 24 hours to prepare and only about 85g of the solid electrolyte material. After particle size testing, the average particle size of the solid electrolyte material prepared by the ball milling process is 9 microns, the particle distribution proportion of the particles with the particle sizes within the range of 6-12 microns is about 50%, and the particle size distribution is relatively dispersed.
In conclusion, the vacuum rapid quenching equipment provided by the invention can obtain the solid electrolyte material with small particle size and concentrated particle size distribution by simultaneously controlling the linear velocity of the roller surface and the circular runout of the roller surface of the rapid quenching roller device. The single-furnace yield of the vacuum rapid quenching equipment provided by the invention can be 50-1000 kg, and can be increased to over 1000kg under the condition of being provided with a large-capacity crucible. Compared with the preparation of solid electrolyte with 5-10 kg magnitude in the prior art, the vacuum rapid quenching equipment provided by the invention can realize the industrial mass production of solid electrolyte materials. The vacuum rapid quenching equipment provided by the invention has the characteristics of compact structure, simplicity in operation, safety and high efficiency.
Furthermore, the vacuum rapid quenching equipment can also be popularized and applied to the preparation of powder for additive manufacturing such as 3D printing and the like, and high-performance metal and alloy ultra-micro powder.
It should be understood by those skilled in the art that various modifications and equivalent arrangements may be made without departing from the spirit and scope of the present invention and it should be understood that the present invention is to be covered by the appended claims.
Claims (10)
1. A vacuum rapid quenching device for preparing a solid electrolyte material is characterized by comprising:
the equipment body comprises a smelting chamber and a quick quenching chamber, and a tundish is arranged between the smelting chamber and the quick quenching chamber; the induction smelting device is arranged in the smelting chamber and is provided with a driving mechanism and a turnover mechanism, and the turnover mechanism can be driven by the driving mechanism to turn over so as to pour the molten liquid in the induction smelting device into the tundish; a quick quenching roller device is arranged in the quick quenching chamber and correspondingly arranged below a discharge hole of the tundish;
the vacuum rapid quenching equipment also comprises a protective feeding device and a material receiving device, wherein the protective feeding device is communicated with the smelting chamber through a feeding channel, and the induction smelting device is correspondingly arranged below the discharging end of the feeding channel; the material receiving device is communicated with the rapid quenching chamber through a discharge channel and can receive and store the solid electrolyte material formed by rapid quenching of the rapid quenching roller device.
2. The vacuum rapid quenching apparatus for producing a solid electrolyte material according to claim 1,
the rapid quenching roller device mainly comprises two mounting seats and a rotating shaft, wherein two ends of the rotating shaft are respectively erected on the two mounting seats, the rotating shaft is provided with a roller surface, and a cooling water channel is arranged in the rotating shaft.
3. The vacuum rapid quenching apparatus for producing a solid electrolyte material according to claim 2,
the linear speed of the roller surface of the rapid quenching roller device is within the range of 1-100 m/s, and the circular runout of the roller surface is controlled within 3 mu m.
4. The vacuum rapid quenching apparatus for producing a solid electrolyte material according to claim 1,
the smelting chamber is provided with an online component monitoring system, and the online component monitoring system comprises an online sampling analysis device and a component adjusting device; the online sampling and analyzing device is used for online sampling and analyzing the molten liquid in the induction smelting device during refining; the component adjusting device is used for providing component adjusting materials to be added when the components of the molten liquid have deviation, and adding the component adjusting materials into the molten liquid in the induction smelting device through the protective feeding device for component adjustment.
5. The vacuum rapid quenching apparatus for producing a solid electrolyte material according to claim 1,
the protective feeding device is used for filling raw materials into the induction melting device under the environment of isolating external atmosphere and moisture; and a feeding isolation valve is arranged on the feeding channel.
6. The vacuum rapid quenching apparatus for producing a solid electrolyte material according to claim 5,
the feeding protection device comprises a feeding chamber and a glove box, and a valve is arranged between the feeding chamber and the glove box; the glove box is a glove box with a weighing function, and is provided with a powdery raw material container interface, a granular container interface and/or a block raw material container interface.
7. The vacuum rapid quenching apparatus for producing a solid electrolyte material according to claim 1,
the interior of the material receiving device is also vacuumized and/or filled with protective gas, and the material receiving device is provided with a water cooling channel; and a discharge valve is arranged on the discharge channel.
8. The vacuum rapid quenching apparatus for producing a solid electrolyte material according to claim 1,
oxygen and moisture monitoring instruments are arranged in the protective feeding device, the smelting chamber, the rapid quenching chamber and the material receiving device.
9. The vacuum rapid quenching apparatus for preparing a solid electrolyte material according to any one of claims 1 to 8, characterized in that,
and a filtering system is arranged at the upstream of the vacuum rapid quenching equipment for discharging gas to the outside.
10. The vacuum rapid quenching apparatus for preparing a solid electrolyte material according to claim 9, wherein the filtering system mainly comprises a housing, a filter screen and an absorbing material; the filter screen is used for removing a part of solid pollutants; the absorption material is one or two of a solvent gas absorption material and a solid gas absorption material and is used for filtering and removing toxic gases possibly contained in the exhaust gas by means of physical adsorption and/or chemical neutralization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011566846.3A CN112683058A (en) | 2020-12-25 | 2020-12-25 | Vacuum rapid quenching equipment for preparing solid electrolyte material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011566846.3A CN112683058A (en) | 2020-12-25 | 2020-12-25 | Vacuum rapid quenching equipment for preparing solid electrolyte material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112683058A true CN112683058A (en) | 2021-04-20 |
Family
ID=75451867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011566846.3A Pending CN112683058A (en) | 2020-12-25 | 2020-12-25 | Vacuum rapid quenching equipment for preparing solid electrolyte material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112683058A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2282950Y (en) * | 1996-11-29 | 1998-06-03 | 中国科学院金属研究所 | Vacuum quick hardening furnace |
| CN1430035A (en) * | 2001-12-30 | 2003-07-16 | 郭锦华 | Vacumn induction electric arc smelting furnace with quick cooling and quenching |
| CN101954485A (en) * | 2009-07-20 | 2011-01-26 | 中国电子科技集团公司第九研究所 | Overflow inducing rapid quenching furnace |
| US20130014860A1 (en) * | 2010-03-29 | 2013-01-17 | Hongwei Li | Method for manufacturing melt-spinning alloys and apparatus thereof |
| CN103611942A (en) * | 2013-12-10 | 2014-03-05 | 河北联合大学 | High-pressure smelting atomizing nitrogen-quenching device and method for utilizing device to produce samarium iron nitrogen alloy powder |
| CN108436094A (en) * | 2018-06-15 | 2018-08-24 | 杭州汉苹科技有限公司 | A kind of neodymium iron boron fast quenching powder for preparing continuously sprays quick quenching furnace with large-scale three chamber pressure differentials |
| CN208600711U (en) * | 2018-06-15 | 2019-03-15 | 杭州汉苹科技有限公司 | It prepares neodymium iron boron fast quenching powder and continuously sprays quick quenching furnace with large-scale three chamber pressure differentials |
-
2020
- 2020-12-25 CN CN202011566846.3A patent/CN112683058A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2282950Y (en) * | 1996-11-29 | 1998-06-03 | 中国科学院金属研究所 | Vacuum quick hardening furnace |
| CN1430035A (en) * | 2001-12-30 | 2003-07-16 | 郭锦华 | Vacumn induction electric arc smelting furnace with quick cooling and quenching |
| CN101954485A (en) * | 2009-07-20 | 2011-01-26 | 中国电子科技集团公司第九研究所 | Overflow inducing rapid quenching furnace |
| US20130014860A1 (en) * | 2010-03-29 | 2013-01-17 | Hongwei Li | Method for manufacturing melt-spinning alloys and apparatus thereof |
| CN103611942A (en) * | 2013-12-10 | 2014-03-05 | 河北联合大学 | High-pressure smelting atomizing nitrogen-quenching device and method for utilizing device to produce samarium iron nitrogen alloy powder |
| CN108436094A (en) * | 2018-06-15 | 2018-08-24 | 杭州汉苹科技有限公司 | A kind of neodymium iron boron fast quenching powder for preparing continuously sprays quick quenching furnace with large-scale three chamber pressure differentials |
| CN208600711U (en) * | 2018-06-15 | 2019-03-15 | 杭州汉苹科技有限公司 | It prepares neodymium iron boron fast quenching powder and continuously sprays quick quenching furnace with large-scale three chamber pressure differentials |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9337476B2 (en) | Lithium sulfide-carbon complex, process for producing the complex, and lithium ion secondary battery utilizing the complex | |
| JP5431809B2 (en) | Lithium ion conductive sulfide glass manufacturing method, lithium ion conductive sulfide glass ceramic manufacturing method, and mechanical milling apparatus for manufacturing sulfide glass | |
| JP5270563B2 (en) | Method for producing lithium ion conductive solid electrolyte | |
| CN108878962B (en) | Sulfide solid electrolyte and preparation method thereof | |
| EP2698856A1 (en) | Method for producing lithium sulfide for lithium ion cell solid electrolyte material | |
| CN111977681B (en) | Sulfide solid electrolyte material, gas phase synthesis method of raw material thereof and application thereof | |
| CN103746141B (en) | A kind of Li-B-N-H compound fast-ion conductor and preparation method thereof | |
| CN112683057B (en) | Multi-module vacuum equipment for preparing solid electrolyte material | |
| CN108878961A (en) | Sulfide solid electrolyte and preparation method thereof and equipment | |
| KR20240005654A (en) | Solid-state lithium ion conductor | |
| CN103762346A (en) | Lithium ion conductor with nanoscale and preparation method thereof | |
| CN114956020A (en) | Li 3 Preparation method of P crystal powder and Li 3 P crystal powder and application thereof | |
| CN114867686B (en) | Lithium ion conductive oxide and use thereof | |
| CN112683058A (en) | Vacuum rapid quenching equipment for preparing solid electrolyte material | |
| CN100527479C (en) | Composite materials of nano-dispersed silicon and tin and methods of making the same | |
| CN112751078B (en) | Preparation method of solid electrolyte material | |
| JP2021150289A (en) | Method for producing sulfide solid electrolyte material | |
| CN112520741A (en) | Production method of carbon-coated silicon powder for lithium battery negative electrode material | |
| CN112670595B (en) | Preparation method of solid-state battery | |
| CN115279688A (en) | Method for producing lithium sulfide | |
| Seo et al. | Characterization of thin-film electrolytes for all solid-state batteries | |
| Yang et al. | An enhanced Li3AlH6 anode prepared by a solid-state ion exchange method for use in a solid-state lithium-ion battery | |
| CN114975988A (en) | Negative electrode layer and fluoride ion secondary battery | |
| WO2023219067A1 (en) | Sulfide-based solid electrolyte powder production method and production device | |
| CN113614038B (en) | Method for producing sulfide-based inorganic solid electrolyte material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |