JP2005108531A - Nonaqueous electrolytic solution compounding device, and manufacturing method of nonaqueous electrolytic solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous electrolytic solution compounding device capable of effective diversified small-quantity production, and a manufacturing method of the nonaqueous electrolytic solution. <P>SOLUTION: The nonaqueous electrolytic solution compounding device 1 comprises a raw material supplying port 21; gas inlets 22; a stirring means 23; an electrolyte container 2 equipped with an electrolyte taking out port 27; an electrolyte supply container 3 having a detachable discharging port 31 at the raw material supplying port 21, filled with high-density electrolytic solution; an additive agent supply container 6 having a detachable discharging port 41 at the raw material supplying port 21, filled with additive agent liquid; a mixed solvent supply container 4 having a detachable discharging port 51 at the raw material supplying port 21, filled with high-density mixed solvent of which, coagulation temperature is adjusted to 20°C or lower; a dilution solvent supply container 5 having a detachable discharging port 61 at the raw material supplying port 21, filled with dilution solvent; an inert gas supplying device 12 connected to the gas inlet 22; and a measuring device 13 measuring a change in the weight of the content of an electrolyte container 2. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a preparation device for preparing a non-aqueous electrolyte for use in a non-aqueous electrolyte battery and a method for producing a non-aqueous electrolyte using the same.

In preparing a non-aqueous electrolyte used for a non-aqueous electrolyte battery, for example, LiPF ₆ is mixed into a mixed solvent obtained by mixing a high dielectric constant solvent such as ethylene carbonate and a diluting solvent such as 1,2-dimethoxyethane. An electrolyte such as vinylene carbonate is dissolved and an additive such as vinylene carbonate is added and mixed (see Patent Document 1).

  The non-aqueous electrolyte is prepared using a stationary preparation equipment 9 in a factory as shown in a conceptual diagram in FIG. The blending equipment 9 includes a stationary large tank 91 (for example, a capacity of about 50 cubic meters) storing each raw material, and a stationary large electrolyte container 92 (for example, a capacity of about 5 cubic meters). Each large tank 91 and the large electrolyte container 92 are connected by a pipe 94. Although not shown, various facilities such as a temperature control facility and an inert gas supply device are connected to the large tank 91 and the large electrolyte container 92.

Then, each raw material stored in the large tank 91 is put into an appropriate amount of a large-sized electrolytic solution container 92 for stationary preparation and mixed with stirring to prepare a large amount of nonaqueous electrolytic solution.
Thus, the stationary non-aqueous electrolyte preparation equipment 9 is premised on a certain amount of mass production.

However, various types of non-aqueous electrolytes having different compositions may be required depending on the performance and application of the non-aqueous electrolyte battery to be obtained. That is, there is a case where the production of the above-mentioned nonaqueous electrolytic solution in a small variety is required.
In such a case, it is necessary to prepare a plurality of types of non-aqueous electrolytes in small amounts by varying the composition such as the mixing ratio of each raw material and the type of additive.

  However, as in the past, when manufacturing multiple types of non-aqueous electrolytes in advance using a large non-aqueous electrolyte preparation device and filling small quantities of product containers for inventory control, delivery after manufacture There are products that take longer to complete, there is a risk that the non-aqueous electrolyte may deteriorate, and if the required type of non-aqueous electrolyte is manufactured after receiving an order from the customer, the composition will be changed for each order. Therefore, there are problems such as troublesome washing of the blender and blending errors.

Moreover, it is necessary to convey the manufactured non-aqueous electrolyte to the battery manufacturing equipment after that. Therefore, when the non-aqueous electrolyte preparation equipment and the battery manufacturing equipment are separated from each other, the non-aqueous electrolyte may be deteriorated during transportation.
In view of this, it is possible to use a small non-aqueous electrolyte preparation device to prepare a plurality of types of non-aqueous electrolytes little by little and supply them to a battery manufacturing facility.

However, there are various problems in making a conventional large-scale compounding equipment into a small compounding device.
That is, for example, there is a problem that waste liquid is generated by washing when switching to a different type of electrolytic solution even if a small-sized preparation device is used. In addition, when a large number of small compounding apparatuses are installed, there is a problem that the operation rate is low.

  Moreover, since the high dielectric constant solvent such as ethylene carbonate may solidify at room temperature, it is necessary to keep the temperature higher than the freezing point. Therefore, conventionally, temperature control equipment is provided in the large tank to prevent the high dielectric constant solvent from solidifying. However, when installing a large number of small compounding devices, it is necessary to supply a high dielectric constant solvent from a large tank to a large number of compounding devices via piping equipped with temperature control equipment, and there is a problem that temperature control equipment is widely required. There is.

Japanese Patent Laid-Open No. 7-122297

  The present invention has been made in view of such conventional problems, and is a non-aqueous electrolyte preparation device that can efficiently perform multi-product and small-quantity production of non-aqueous electrolytes, and a non-aqueous electrolyte using the same. It is intended to provide a manufacturing method.

The first invention is provided with a raw material inlet for introducing raw materials and a gas inlet for introducing inert gas at the top, a stirring means for stirring the raw materials, and non-water prepared inside An electrolytic solution container having an electrolytic solution outlet for taking out the electrolytic solution;
An electrolyte supply container filled with a high-concentration electrolyte solution in which a solid electrolyte is dissolved in a dissolving solvent;
An additive supply container filled with a high-concentration additive solution containing an additive and a diluting solvent;
A mixed solvent having a discharge port that can be attached to and detached from the raw material charging port of the electrolytic solution container and containing a high-dielectric solvent and a diluting solvent and a high-concentration mixed solvent adjusted to a solidification temperature of 20 ° C. or lower A supply container;
A dilution solvent supply container having a discharge port detachably attached to the raw material charging port of the electrolyte container and filled with a dilution solvent;
An inert gas supply device connected to the gas inlet of the electrolyte container, press-fitting an inert gas into the electrolyte container, and pumping the non-aqueous electrolyte from the electrolyte outlet;
A non-aqueous electrolyte preparation device comprising a measuring device for measuring a change in content weight of the electrolyte container,
The electrolyte solution container, the electrolyte supply container, the additive supply container, the mixed solvent supply container, and the dilution solvent supply container are non-aqueous electrolysis characterized in that they are made of a hermetically sealed container capable of preventing intrusion of outside air. It exists in the liquid preparation apparatus (Claim 1).

Next, the effects of the present invention will be described.
As described above, the electrolyte supply container, the mixed solvent supply container, the dilution solvent supply container, and the additive supply container have a discharge port that can be attached to and detached from the raw material charging port of the electrolyte solution container. Therefore, each container may be connected to the electrolytic solution container when the raw materials are charged, and each container and the electrolytic solution container can be made independent in other cases. Therefore, the non-aqueous electrolyte preparation device can be easily moved.
And it becomes possible to arrange each component comparatively freely, for example, since it becomes easy to arrange also in the vicinity of the battery manufacturing equipment, etc., it is used for battery manufacture without deteriorating the prepared non-aqueous electrolyte. be able to.

  As described above, the non-aqueous electrolyte preparation apparatus includes the electrolyte container, the electrolyte supply container provided with a detachable discharge port at the raw material charging port of the electrolyte container, the mixed solvent supply container, It has a dilution solvent supply container and the additive supply container. These containers are sealed containers.

Therefore, it can prevent that air and a water | moisture content mix in said each raw material. In addition, the non-aqueous electrolyte solution is prepared while preventing air and moisture from being mixed by connecting the containers to the electrolyte solution container through the discharge port and introducing appropriate amounts of the respective raw materials into the electrolyte solution container. Can do.
And since each raw material in each said container can be correctly poured into an electrolyte solution container by a proper amount using the above-mentioned measuring device, even when preparing a small amount of non-aqueous electrolyte, A water electrolyte can be easily obtained.

The high-concentration mixed solvent in the mixed solvent supply container contains a high dielectric constant solvent and a diluting solvent, and the coagulation temperature is adjusted to 20 ° C. or lower. This can prevent the high dielectric constant solvent from being supplied to the electrolyte container in a solidified state.
Moreover, since it is not necessary to equip the said mixed solvent supply container with temperature control equipment etc., movement and conveyance of this mixed solvent supply container become easy.

  Moreover, the high concentration additive solution with which the additive supply container is filled contains an additive and a diluting solvent. Therefore, since the additive is charged into the electrolytic solution container in a diluted solution state, fine adjustment of the charged amount is facilitated, and small-scale production of the nonaqueous electrolytic solution can be facilitated.

  Moreover, since the said preparation apparatus has the said inert gas supply apparatus, the said electrolyte solution container can be made into inert gas atmosphere. Thereby, the contact of oxygen and water | moisture content to the said non-aqueous electrolyte and its raw material can be prevented. Moreover, the non-aqueous electrolyte produced in a small amount can be easily taken out from the electrolyte container by press-fitting the inert gas into the electrolyte container with the inert gas supply device.

  Further, since the electrolyte supply container is filled with a high concentration electrolyte solution in which the solid electrolyte is dissolved in a dissolution solvent, the electrolyte is charged into the electrolyte container in a solution state and mixed with other raw materials. . Therefore, heat generation during mixing in the electrolyte container can be suppressed. Therefore, it is not particularly necessary to cool the electrolyte container, and it is not particularly necessary to provide temperature control means. Thereby, size reduction, simplification, and cost reduction of the non-aqueous electrolyte preparation device can be realized.

  As described above, according to the present invention, it is possible to provide a non-aqueous electrolyte preparation device that can efficiently produce a variety of small quantities of non-aqueous electrolytes.

According to a second aspect of the present invention, a nonaqueous electrolytic solution is prepared by automatically mixing a solid electrolyte, a high concentration mixed solvent, a diluting solvent, and a high concentration additive solution using the above-described preparation apparatus, The present invention resides in a method for producing a nonaqueous electrolytic solution, wherein the electrolytic solution is automatically analyzed.
ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the nonaqueous electrolyte which can perform the multi-product small quantity production of a nonaqueous electrolyte efficiently can be provided.

In the first invention (Invention 1), the inner shape of the electrolyte container is preferably a substantially cylindrical shape. And when the height is set to L and the diameter is set to D, it is preferable that L / D will be set to 1-5. In this case, it is possible to cope with various production amounts of the nonaqueous electrolytic solution. In the case of L / D <0.5, it may be difficult to change the amount of the nonaqueous electrolytic solution over a wide range. On the other hand, in the case of L / D> 10, the mixing characteristics are deteriorated, and the production of the electrolytic solution container may be difficult.
Moreover, the capacity | capacitance of the said electrolyte solution container can be 1-1000 liters.

The stirring means is preferably disposed in a 20 volume% space from below in the electrolyte container.
In this case, even when the amount of the non-aqueous electrolyte is small, it can be sufficiently stirred, and a small amount of the non-aqueous electrolyte can be easily prepared.

Furthermore, the electrolyte container preferably has two or more stages of stirring means.
As a result, when a relatively large amount of non-aqueous electrolyte is prepared, the non-aqueous electrolyte can be stirred from the lower stirring means to the upper stirring means. When preparing the liquid, the non-aqueous electrolyte can be stirred using the lower stirring means. Thus, efficient stirring can be performed according to the amount of the non-aqueous electrolyte.

Further, as the stirring means, a paddle blade, a turbine blade, a blade having three retreated blades, a magnetic stirrer, or the like can be used. The wings such as the paddle wing are preferably arranged in two or more upper and lower stages, and pitch paddle wings whose wing surfaces are inclined can also be used. When using the above magnetic stirrer, it is preferable to subject the magnetic stirrer to a surface treatment such as Teflon (registered trademark) processing so that the metal powder is not mixed into the non-aqueous electrolyte due to the collision between the inner wall of the electrolytic solution container and the stirrer. .
Further, as the agitation means, means such as air flow agitation using nitrogen gas or the like, ultrasonic agitation from the outside of the electrolyte container, and rotation of the electrolyte container itself can be used. Not.

In addition, the electrolyte solution container, the electrolyte supply container, the mixed solvent supply container, the dilution solvent supply container, and the additive supply container may be any material that is inert to the contents, such as stainless steel (SUS304 or the like). ) Can be used.
The high concentration electrolyte solution may be purified in advance by dissolving the solid electrolyte in a dissolving solvent such as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), or diethyl carbonate (DEC). it can.

The high-concentration mixed solvent is preferably adjusted so as to have a slightly higher concentration than the concentration of the high dielectric constant solvent in the finally obtained nonaqueous electrolytic solution.
Examples of the dilution solvent include chain carbonates such as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC), tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1, Examples include ethers such as 2-dibutoxyethane, lactones such as γ-butyrolactone, nitriles such as acetonitrile, esters such as methyl propionate, and amides such as dimethylformamide. These dilution solvents may be used alone or in combination of two or more.
Moreover, the same kind can be used for the dilution solvent contained in the said high concentration mixed solvent, the dilution solvent contained in the additive solution, and the dilution solvent with which the said dilution solvent supply container was filled. .

  Examples of the additive include an additive for positive electrode protection, negative electrode protection, overcharge prevention, wettability improvement, and the like. Specifically, succinic anhydride (Suc), vinylene carbonate (VC), vinylene ethylidene carbonate, ethylene sulfide (ES), sulfolane (Sul), propane sultone, lithium trifluoromethane, sulfonic acid imide, methoxyethyl methyl carbonate, Examples include methylphenyl carbonate, t-amylbenzene, cyclohexylbenzene, biphenyl (BP), o-terphenyl, and dibenzofuran.

Moreover, it is preferable that melting | fusing point is 20 degrees C or less so that the said additive can produce the said high concentration additive solution of a higher concentration.
The solidification temperature of the high-concentration mixed solvent is more preferably 0 ° C. or lower. In this case, coagulation of the high-concentration mixed solution can be prevented even in winter or cold regions, and the non-aqueous electrolyte can be easily prepared.

Examples of the inert gas supplied from the inert gas supply device include nitrogen and argon.
The moisture content of the inert gas is preferably 50 ppm or less, and more preferably 10 ppm.

Further, the weighing device measures the content weight of the electrolyte container at the time of charging each raw material, even if the content weight of the mixed solvent supply container, dilution solvent supply container, and additive supply container is directly measured. The change in the weight of the content of the mixed solvent supply container or the like may be measured from the change.
In the case of directly weighing the contents of the mixed solvent supply container, dilution solvent supply container, and additive supply container, the measuring device may be, for example, a maximum measurable weight of 500 kg and a measurement accuracy of 1/3000 to 1 / 10,000 is used. When measuring the weight of the content of the dissolving solvent for the solid electrolyte, for example, a measuring device having a maximum measurable weight of 5 t and a measurement accuracy of 1 / 3,000 to 1/10000 is used.

  In addition, for example, a variety of non-aqueous electrolytes can be manufactured easily in the vicinity of a battery manufacturing facility using the above-described blending apparatus in response to the demands of the battery manufacturer. It is preferable that the manufactured non-aqueous electrolyte solution is subjected to simple measurement of at least specific gravity, moisture, and acid content directly or indirectly and the quality is confirmed on site.

The solid electrolyte is preferably a lithium-based electrolyte (claim 2).
In this case, the lithium battery using the obtained non-aqueous electrolyte has advantages such as higher energy density and higher voltage than other batteries.
The solid electrolyte is preferably composed of one or more of LiPF ₆ , LiBF ₄ , and LiClO ₄ . In this case, a nonaqueous electrolytic solution exhibiting a high conductivity can be obtained. The solid electrolyte has an advantage that it is easily available industrially.

Further, at least one of the electrolyte supply container, the mixed solvent supply container, the dilution solvent supply container, and the additive supply container has a gas inlet for connection to an inert gas supply device in the vicinity of the upper part. It is preferable that the contents can be transferred from the discharge port to the electrolytic solution container while supplying an inert gas from the gas introduction port.
In this case, the high-concentration electrolyte solution, the high-concentration mixed solvent, the dilution solvent, or the high-concentration additive solution can be easily put into the electrolytic solution container without contacting oxygen or moisture. .

  In addition, when introducing a high concentration electrolyte solution, a high concentration mixed solvent, a diluting solvent, and an additive solution into an electrolytic solution container, an inert gas is supplied to each container, and each raw material is converted into a dissolving solvent. It is preferable to pump.

The high dielectric constant solvent is preferably ethylene carbonate.
In this case, the non-aqueous electrolyte battery not only has high conductivity as a non-aqueous electrolyte, but also has a relatively low reactivity with a negative electrode material such as graphite, and the deterioration of the non-aqueous electrolyte and the negative electrode material is small. Can be obtained.

In addition to ethylene carbonate (EC), cyclic carbonates such as propylene carbonate and butylene carbonate can be used as the high dielectric constant solvent.
Moreover, the said high dielectric constant solvent may be used by 1 type, or may be used in combination of 2 or more type.

Moreover, it is preferable that the said inert gas supply apparatus consists of an air separation nitrogen apparatus which can supply nitrogen gas with a purity of 99% or more.
In this case, oxygen and moisture can be further prevented from being mixed into the non-aqueous electrolyte, and the inert gas can be supplied at a lower cost.

Moreover, the said preparation apparatus can also be mounted in a conveying apparatus.
In this case, for example, the preparation device can be moved to a plurality of distant battery manufacturing facilities, and a desired non-aqueous electrolyte can be prepared and provided.
In addition, when the above-described blending device is mounted on a transport device, for example, a magnetic stirrer that does not require a bearing, such as a solid electrolyte that ensures sealing of a solid solvent by sufficiently considering the seal of a bearing of a stirring means such as a paddle blade, etc. It is preferable to use the stirring device.

(Example 1)
A non-aqueous electrolyte preparation device and a non-aqueous electrolyte manufacturing method according to an embodiment of the present invention will be described with reference to FIGS.
As shown in FIG. 1, the non-aqueous electrolyte preparation device 1 includes an electrolyte container 2, an electrolyte supply container 3, a mixed solvent supply container 4, a dilution solvent supply container 5, and an additive supply container 6. And an inert gas supply device 12 and a metering device 13.

As shown in FIGS. 2 and 3, the electrolyte container 2 is provided with a raw material inlet 21 for introducing a raw material and a gas inlet 22 for introducing an inert gas at an upper portion thereof, for stirring the raw material. The agitation means 23 is provided inside, and a liquid supply / take-out port 25 for taking out the non-aqueous electrolyte 7 prepared inside is provided. Moreover, the said electrolyte solution container 2 can be used as a product can as it is.
Further, as shown in FIG. 1, the electrolyte supply container 3 has a discharge port 31 that can be attached to and detached from the raw material input port 21 of the electrolyte solution container 2, and is filled with a high concentration electrolyte solution in which a solid electrolyte is dissolved in a dissolving solvent. doing.

The mixed solvent supply container 4 has a discharge port 41 that can be attached to and detached from the raw material charging port 21 of the electrolytic solution container 2, contains a high dielectric constant solvent and a diluting solvent, and is adjusted to a solidification temperature of 20 ° C. or lower. Packed with high-concentration mixed solvent.
The dilution solvent supply container 5 has a discharge port 51 that can be attached to and detached from the raw material charging port 21 of the electrolytic solution container 2 and is filled with the dilution solvent.
The additive supply container 6 has a discharge port 61 that can be attached to and detached from the raw material charging port 21 of the electrolytic solution container 2 and is filled with a high concentration additive solution containing an additive and a diluent solvent.

The inert gas supply device 12 is connected to the gas introduction port 22 in the upper part of the electrolytic solution container 2 via a joint 262 and presses the inert gas into the electrolytic solution container 2 to supply the nonaqueous electrolytic solution 7 as a liquid. It can be pumped from the cum outlet 25.
The measuring device 13 measures the change in the weight of the contents of the electrolyte container 2.
The electrolyte container 2, the electrolyte supply container 3, the mixed solvent supply container 4, the dilution solvent supply container 5, and the additive supply container 6 are sealed containers that can prevent the intrusion of outside air.

  As shown in FIGS. 2 to 4, the electrolytic solution container 2 is provided with a rotary feeder 24 at the top. The rotary feeder 24 includes a lower step portion 241 connected to the liquid supply / takeout port 25 at the upper portion of the electrolyte container 2 via a joint 261, and an upper step portion 242 that is rotatable with respect to the lower step portion 241. Have. The upper stage portion 242 is provided with a plurality of joints with valves, part of which is the raw material inlet 21 and the other part of which is an electrolyte outlet 27. Further, the lower step portion 241 is formed with a lower through nozzle 243 that communicates with the liquid supply / takeout port 25, and the upper step portion 242 communicates with the raw material inlet 21 or the electrolyte solution outlet 27, respectively. A plurality of upper penetrating nozzles 244 are provided.

The upper through nozzle 244 is configured to sequentially communicate with the lower through nozzle 243 by rotating the upper stage 242 with respect to the lower stage 241.
Further, reference numeral 29 in FIG. 2 is a joint for detaching a siphon tube 251 and a stirring means 23 described later from the electrolyte container 2.

The electrolyte container 2 is, for example, a substantially cylindrical container having a capacity of 200 liters, an inner diameter D = 600 mm, and a height L = 800 mm, and is made of stainless steel (SUS304 or the like).
In addition, a siphon tube 251 extending to the vicinity of the bottom of the electrolyte container 2 is connected to the liquid supply / take-out port 25. The stirring means 23 is composed of a rotor that is supported by the siphon tube 251 and rotates. The rotor (stirring means 23) is made of Teflon (registered trademark) coated with an iron core, and is rotated by a magnetic stirrer 230 disposed on the lower side of the electrolyte container 2.

The stirring means 23 is disposed in a 20 volume% space from below in the electrolyte container 2.
Further, as shown in FIGS. 2 and 3, the electrolytic solution container 2 has a guard wall 28 erected from the outer periphery of the upper surface of the container so as to protect the liquid supply / take-out port 25 and the gas introduction port 22. The other guard (electrolyte supply container 3 etc.) is also provided with the same guard wall.

  The electrolyte supply container 3, the additive supply container 6, the mixed solvent supply container 4, and the dilution solvent supply container 5 have, for example, a substantially cylindrical shape with a capacity of 200 liters, an inner diameter D = 600 mm, and a height L = 800 mm. The container is made of stainless steel (SUS304 or the like).

  As shown in FIGS. 1 and 6, the electrolyte supply container 3, the mixed solvent supply container 4, the diluting solvent supply container 5, and the additive supply container 6 are each in the vicinity of the upper portion of the inert gas supply device 12. Gas inlets 32, 42, 52, 62 for connection to the By supplying nitrogen gas, which is an inert gas, from the gas inlets 32, 42, 52, 62, the contents can be pumped from the discharge ports 31, 41, 51, 61 to the electrolyte container 2. It is configured as follows. FIG. 6 shows a cross-sectional view of the mixed solvent supply container 4, but the electrolyte supply container 3, the diluted solvent supply container 5, and the additive solution supply container 6 also have the same structure.

  This structure will be described more specifically with reference to FIG. 6 using the mixed solvent supply container 4 as a representative example. The discharge port 41 and the gas introduction port 42 are provided in the upper part of the container, and narrow tubes 411 and 421 extend from the discharge port 41 and the gas introduction port 42 toward the inside of the container, respectively. The narrow tube 411 extending from the discharge port 41 has a lower end 412 positioned near the bottom of the container, and the narrow tube 421 extended from the gas inlet 42 has a lower end 423 near the upper portion of the container. It is located above the liquid level 49 of the contents.

As shown in FIG. 1, the discharge ports 31, 41, 51, 61 in the electrolyte supply container 3, the mixed solvent supply container 4, the dilution solvent supply container 5, and the additive supply container 6 are respectively connected to the electrolyte solution by a flexible tube 14. It is connected to the raw material inlet 21 in the container 2. In addition, each component in the said preparation apparatus 1 is connected by the flexible tube 14, such as between the said inert gas supply apparatus 12 and the electrolyte solution container 2, respectively.
Moreover, each component in the said preparation apparatus 1, such as the electrolyte solution container 2 and the electrolyte supply container 3, can be moved freely instead of a stationary type.

In addition, an automatic analyzer 18 for automatically analyzing the prepared nonaqueous electrolytic solution 7 is connected to the electrolytic solution outlet 27.
The inert gas supply device 12 includes an air separation nitrogen device that can supply nitrogen gas having a purity of 99% or more.

The measuring device 13 measures the weight change of the electrolytic solution container 2 to measure the supply amount of each raw material. The weighing device 1 has a maximum measurable weight of 300 kg and a measurement accuracy of 1/3000 to 1/6000.
Moreover, the said compounding apparatus 1 is comprised so that a series of compounding processes can be automatically controlled by the computer 17. FIG. In addition, the code | symbol 171 in FIG. 1 is a pressure control system for operating the automatic valves 191 and 192 by detecting the pressure in the container.

In the high-concentration mixed solvent, ethylene carbonate (EC) is used as the high dielectric constant solvent, and ethyl methyl carbonate (EMC) is used as the dilution solvent.
Further, the dilution solvent contained in the high-concentration mixed solvent, the dilution solvent contained in the additive solution, and the dilution solvent filled in the dilution solvent supply container 5 are of the same type, that is, ethyl. Methyl carbonate (EMC) is used.

  The concentration of the high dielectric constant solvent in the high concentration mixed solvent is preferably slightly higher than the concentration of the high dielectric constant solvent in the final nonaqueous electrolytic solution 7. For example, when the concentration of the high dielectric constant solvent in the nonaqueous electrolytic solution 7 is 20 to 50% by weight, the concentration of the high dielectric constant solvent (EC) in the high concentration mixed solvent is preferably 30 to 70% by weight. Is 40-60% by weight.

  The high dielectric constant solvent and the dilution solvent are purified in advance by a method such as distillation or adsorption treatment. In the case of distillation, the conditions such as the reflux ratio, the rectification temperature, and the degree of vacuum are set appropriately. Moreover, when performing an adsorption process, the method of processing by adsorption agents, such as a silica gel, activated carbon, activated alumina, and special molecular sieve, is mentioned.

  As the additive, vinylene carbonate (VC) for the purpose of improving performance such as battery cycle characteristics and cyclohexylbenzyl (CHB) for the purpose of improving safety are used. These additives are filled in different additive supply containers 6.

Next, a method for preparing a non-aqueous electrolyte using the non-aqueous electrolyte preparation device 1 will be described.
First, as shown in FIG. 5, each component of the said preparation apparatus 1 is prepared.
That is, the electrolyte supply container 3 is filled with a high-concentration electrolyte solution purified in advance by dissolving the solid electrolyte in the dissolving solvent in a factory in advance to form a master batch.
The mixed solvent supply container 4 is preliminarily refined by precision distillation, adsorption purification, etc. at the factory, and mixed with a diluting solvent to adjust the coagulation temperature to 20 ° C. or lower, and is filled into a master batch. Keep it.

The additive supply container 6 is filled with a high-concentration additive solution purified in advance by dissolving the additive in a diluting solvent in a factory, and is made into a master batch.
Also, as shown in FIG. 5, a plurality of empty electrolyte containers 2 are prepared.
In addition, each container is a container that is cleaned and maintained at an inner surface and an outer surface at a factory, and nitrogen is pressurized and filled to about 0.05 MPa.

In addition, the computer 17 that automatically controls the blending apparatus 1 previously stores the brand of the non-aqueous electrolyte 7, the production amount, the type and composition of the electrolyte solution container 2, the allowable impurity concentration, the production amount for each container, and the like. Register several patterns. Then, the brand of the non-aqueous electrolyte 7 to be blended, the production amount, the type of the electrolyte container, and the blending order of the brand are input to the computer 17.
Thereafter, the automatic blending of the non-aqueous electrolyte 7 is started by inputting a blending start signal.

In automatic blending, a predetermined electrolyte container 2 is automatically set in a load cell as the weighing device 13, and the weight of the empty electrolyte container 2 is measured.
Thereafter, the rotary feeder 24 is automatically set in the electrolytic solution container 2.
Next, in order to release the pressure inside the electrolytic solution container 2, the vent valve 191 is opened to perform depressurization.

After depressurization, each raw material is sequentially supplied from the electrolyte supply container 3, the mixed solution supply container 4, the dilution solvent supply container 5, and the additive supply container 6 through the rotary feeder 24, respectively, in the specified amount, and the electrolyte container 2. It is thrown into. The charging is performed while weighing by the weighing device 13.
After adding each raw material, the stirring means 23 is started, and stirring and mixing are performed for 5 to 10 minutes.

After stirring and mixing, the supply valve 192 is opened, and the inert gas (nitrogen gas) is supplied from the inert gas supply device 12 to the electrolyte container 2 and pressurized to about 0.05 MPa.
Next, the non-aqueous electrolyte 7 is supplied to the automatic analyzer 18 from the liquid supply / extraction port 25 of the electrolyte solution container 2 through the electrolyte solution extraction port 27 of the rotary feeder 24, and automatic analysis is performed. For example, the composition of the non-aqueous electrolyte 7 and the concentration of H ₂ O, HF, or heavy metal as impurities are analyzed.

After the analysis is completed, an inert gas is pressurized and supplied from the electrolyte outlet 27 provided in the rotary feeder 24 to the siphon tube 251 of the electrolyte container 2 to convert the nonaqueous electrolyte 7 in the tube into the inert gas. replace.
Next, the electrolytic solution container 2 in which the nonaqueous electrolytic solution 7 is purified is separated from the rotary feeder 24 and moved to the storage area.
The rotary feeder 24 is washed with a small amount of solvent used for the next brand in order to prevent contamination of the next brand with the non-aqueous electrolyte. The cleaning waste liquid is stored in the waste liquid container 101.

Next, the function and effect of this example will be described.
As described above, the electrolyte supply container 3, the mixed solvent supply container 4, the dilution solvent supply container 5, and the additive supply container 6 are detachably attached to the raw material input port 21 of the electrolyte solution container 2. , 41, 51, 61. Therefore, each container may be connected to the electrolyte container 2 when each raw material is charged, and each container and the electrolyte container 2 can be made independent in other cases. Therefore, the non-aqueous electrolyte preparation device 1 can be easily moved.
And it becomes possible to arrange each component relatively freely, and for example, it becomes easy to arrange in the vicinity of the battery manufacturing equipment, etc., so that it is used for battery manufacture without deteriorating the prepared non-aqueous electrolyte 7. can do.

  As described above, the non-aqueous electrolyte preparation device 1 has the electrolyte container 2 and the discharge ports 31, 41, 51, 61 detachably attached to the raw material inlet 21 of the electrolyte container 2, respectively. It has a supply container 3, the mixed solvent supply container 4, the dilution solvent supply container 5, and the additive supply container 6. These containers are sealed containers.

Therefore, it can prevent that air and a water | moisture content mix in said each raw material. In addition, by connecting the containers to the electrolyte solution container 2 at the discharge ports 31, 41, 51, 61 and introducing appropriate amounts of the respective raw materials into the electrolyte solution container 2, while preventing the entry of air and moisture. The nonaqueous electrolyte solution 7 can be prepared.
And since each raw material in each said container can be correctly injected | thrown-in to the electrolyte solution container 2 by a suitable amount correctly using the said measuring device 13, even when preparing a small amount of non-aqueous electrolyte solution 7, it is desired. The nonaqueous electrolytic solution 7 having the composition can be easily obtained.

The high-concentration mixed solvent in the mixed solvent supply container 4 contains a high dielectric constant solvent and a diluting solvent, and the coagulation temperature is adjusted to 20 ° C. or lower. Thereby, it can prevent that the said high dielectric constant solvent is supplied to the electrolyte solution container 2 in the solidified state.
Moreover, since it is not necessary to equip the said mixed solvent supply container 4 with temperature control equipment etc., this mixed solvent supply container 4 becomes easy to move and convey.

Moreover, the high concentration additive solution with which the additive supply container 6 is filled contains an additive and a diluting solvent. Therefore, since the additive is charged into the electrolytic solution container 2 in a diluted solution state, fine adjustment of the charged amount is facilitated, and small-scale production of the nonaqueous electrolytic solution 7 can be facilitated.
In addition, since small-scale production is facilitated in this way, for example, it becomes easy to produce only the non-aqueous electrolyte for use the next day, so that a fresh non-aqueous electrolyte can be used.

  Moreover, since the said preparation apparatus 1 has the said inert gas supply apparatus 12, the said electrolyte solution container 2 can be made into inert gas atmosphere. Thereby, the contact of oxygen and moisture to the non-aqueous electrolyte 7 and its raw material can be prevented. Moreover, the non-aqueous electrolyte 7 produced in a small amount can be easily taken out from the electrolyte container 2 by injecting the inert gas into the electrolyte container 2 by the inert gas supply device 12.

  In addition, since the electrolyte supply container 2 is filled with a high concentration electrolyte solution in which the solid electrolyte is dissolved in a dissolving solvent, the electrolyte is charged into the electrolyte container 2 in a solution state and mixed with other raw materials. Is done. Therefore, heat generation during mixing in the electrolytic solution container 2 can be suppressed. Therefore, it is not particularly necessary to cool the electrolytic solution container 2, and it is not particularly necessary to provide temperature control means. Thereby, size reduction, simplification, and cost reduction of the non-aqueous electrolyte preparation device 1 can be realized.

Moreover, since the non-aqueous electrolyte 7 can be obtained by automatic preparation as described above, for example, a desired non-aqueous electrolyte 7 can be automatically prepared simply by specifying a brand. Therefore, the nonaqueous electrolytic solution 7 can be easily manufactured. Further, according to such automatic blending, production data, analysis values and the like can be managed remotely.
Moreover, since the said electrolyte solution container 2 can also be used as a storage container of this nonaqueous electrolyte solution 7 as it is after preparing the nonaqueous electrolyte solution 7, it can improve production efficiency.

In addition, since the solid electrolyte is a lithium-based electrolyte, a lithium battery having a high energy density and a high voltage can be obtained using the obtained nonaqueous electrolytic solution 7.
Further, the solid electrolyte, since made of LiPF _6, it is possible to obtain a non-aqueous electrolyte solution 7 which shows high conductivity. The solid electrolyte has an advantage that it is easily available industrially.

The electrolyte supply container 3, the mixed solvent supply container 4, the dilution solvent supply container 5, and the additive supply container 6 have the gas inlets 32, 42, 52, 62, and the gas inlet The contents can be transferred from the discharge ports 31, 41, 51, 61 to the electrolytic solution container 2 while supplying an inert gas from 32, 42, 52, 62.
Therefore, the solid electrolyte can be easily poured into the dissolving solvent without bringing the solid electrolyte, the high concentration mixed solvent, the dilution solvent, or the high concentration additive solution into contact with oxygen or moisture.

  In addition, since the high dielectric constant solvent is ethylene carbonate, not only high electrical conductivity can be obtained as the non-aqueous electrolyte solution 7, but also the reactivity with the negative electrode material such as graphite is relatively low. A nonaqueous electrolyte battery with little deterioration of the negative electrode material can be obtained.

  The inert gas supply device 12 includes an air separation nitrogen device that can supply nitrogen gas having a purity of 99% or more. Therefore, it is possible to further prevent oxygen and moisture from being mixed into the nonaqueous electrolytic solution 7 and to supply the inert gas at a lower cost.

  As described above, according to this example, it is possible to provide a non-aqueous electrolyte preparation apparatus and a non-aqueous electrolyte manufacturing method capable of efficiently performing a large variety of non-aqueous electrolytes in small quantities.

(Example 2)
This example is an example of non-aqueous electrolytes of various compositions that can be prepared using the preparation apparatus according to the present invention.
That is, as shown in Tables 1 and 2, the nonaqueous electrolytic solution is prepared by adjusting the electrolyte, the high dielectric constant solvent, the diluting solvent, and various additives to various concentrations. When preparing the preparation, the high-concentration electrolyte solution, the high-concentration mixed solvent, the diluting solvent, and the high-concentration additive solution are appropriately adjusted as shown in Tables 1 and 2 and then introduced into the electrolytic solution container. To do.

Moreover, two types of high concentration electrolyte solutions were used as follows. Represented as high concentration electrolyte solutions A and B, respectively.
That is, the non-aqueous electrolyte of composition 1 shown in Table 1 is a high-concentration electrolyte solution A in which 14.0 kg of LiPF ₆ is dissolved in 44.5 kg of ethyl methyl carbonate (EMC), and 9.4 kg of LiPF ₆ in 84%. The high-concentration electrolyte solution B dissolved in 2 kg of EMC is put into the electrolytic solution container 2. Furthermore, a high-concentration mixed solvent in which ethylene carbonate (EC) and ethylmethyl carbonate (EMC) were mixed in a ratio of 14.4 kg each, a diluted solvent consisting of 15.2 kg EMC, and 2.0 kg anhydrous succinate A high-concentration additive solution in which acid (Suc) is dissolved in 2.0 kg of EMC is charged into the electrolytic solution container 2. And these are stirred and mixed.

As a result, as the final composition (composition 1), LiPF ₆ is 11.7% by weight, EC is 49.3% by weight, EMC is 38.0% by weight, and Suc is 1.0% by weight.
Moreover, the freezing point of the high-concentration mixed solvent before being charged into the electrolytic solution container is 7 ° C.

  Further, for the non-aqueous electrolyte solution of composition 2 shown in Table 2, high concentration electrolyte solutions A and B, high concentration mixed solvent, dilution solvent, and high concentration addition of the composition and amount shown in the same table as above The agent solution is produced by putting it in the electrolytic solution container 2. Moreover, the freezing point of the high-concentration mixed solvent before being charged into the electrolytic solution container is 7 ° C.

  Thus, non-aqueous electrolytes having various compositions can be prepared using the preparation apparatus of the present invention. In addition, non-aqueous electrolytes having various compositions other than those shown in this example can also be prepared using the preparation apparatus of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory diagram of a non-aqueous electrolyte preparation device in Example 1. 1 is a perspective view of an electrolyte container in Example 1. FIG. 1 is a cross-sectional view of an electrolytic solution container in Example 1. FIG. FIG. 3 is a perspective view of a rotary feeder in the first embodiment. The conceptual diagram of the manufacturing method of the non-aqueous electrolyte in Example 1. FIG. Sectional drawing of the mixed solvent supply container in Example 1. FIG. The conceptual diagram of the preparation equipment of the non-aqueous electrolyte in a prior art example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Preparation apparatus 12 Inert gas supply apparatus 13 Metering apparatus 2 Electrolyte container 21 Raw material inlet 22 Gas inlet 23 Stirring means 3 Electrolyte supply container 4 Mixed solvent supply container 5 Dilution solvent supply container 6 Additive supply container 31,41, 51, 61 Discharge port 7 Non-aqueous electrolyte

Claims (6)

A raw material input port for introducing the raw material and a gas inlet port for introducing an inert gas are provided at the top, and a stirring means for stirring the raw material and a non-aqueous electrolyte prepared inside are taken out. An electrolyte container having an electrolyte outlet;
An electrolyte supply container filled with a high-concentration electrolyte solution in which a solid electrolyte is dissolved in a dissolving solvent;
An additive supply container filled with a high-concentration additive solution containing an additive and a diluting solvent;
A mixed solvent having a discharge port that can be attached to and detached from the raw material charging port of the electrolytic solution container and containing a high-dielectric solvent and a diluting solvent and a high-concentration mixed solvent adjusted to a solidification temperature of 20 ° C. or lower A supply container;
A dilution solvent supply container having a discharge port detachably attached to the raw material charging port of the electrolyte container and filled with a dilution solvent;
An inert gas supply device connected to the gas inlet of the electrolyte container, press-fitting an inert gas into the electrolyte container, and pumping the non-aqueous electrolyte from the electrolyte outlet;
A non-aqueous electrolyte preparation device comprising a measuring device for measuring a change in content weight of the electrolyte container,
The electrolyte solution container, the electrolyte supply container, the additive supply container, the mixed solvent supply container, and the dilution solvent supply container are non-aqueous electrolysis characterized in that they are made of a hermetically sealed container capable of preventing intrusion of outside air. Liquid preparation device.   The non-aqueous electrolyte preparation device according to claim 1, wherein the solid electrolyte is a lithium-based electrolyte.   3. The gas for connecting at least one of the electrolyte supply container, the mixed solvent supply container, the dilution solvent supply container, and the additive supply container to the inert gas supply device in the vicinity of the upper part according to claim 1 or 2. A non-aqueous electrolyte comprising an inlet and configured to transfer contents from the outlet to the electrolyte container while supplying an inert gas from the gas inlet Preparation equipment.   4. The non-aqueous electrolyte preparation device according to claim 1, wherein the high dielectric constant solvent is ethylene carbonate.   The non-aqueous electrolyte preparation according to any one of claims 1 to 4, wherein the inert gas supply device includes an air separation nitrogen device capable of supplying nitrogen gas having a purity of 99% or more. apparatus.   Using the blending apparatus according to any one of claims 1 to 5, a solid electrolyte, a high concentration mixed solvent, a dilution solvent, and a high concentration additive solution are automatically mixed to prepare a non-aqueous electrolyte. A method for producing a nonaqueous electrolytic solution, wherein the obtained nonaqueous electrolytic solution is automatically analyzed.

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