CN112064063A - Method for improving current efficiency of metal lithium electrolysis - Google Patents
Method for improving current efficiency of metal lithium electrolysis Download PDFInfo
- Publication number
- CN112064063A CN112064063A CN202010886397.4A CN202010886397A CN112064063A CN 112064063 A CN112064063 A CN 112064063A CN 202010886397 A CN202010886397 A CN 202010886397A CN 112064063 A CN112064063 A CN 112064063A
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- China
- Prior art keywords
- current efficiency
- humidity
- electrolytic cell
- air
- electrolysis
- 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.)
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005070 sampling Methods 0.000 claims description 4
- 238000005192 partition Methods 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000011112 process operation Methods 0.000 abstract 1
- 239000003570 air Substances 0.000 description 19
- 239000002994 raw material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 4
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to the technical field of molten salt electrolysis, and particularly relates to a method for improving the electrolytic current efficiency of metal lithium, which is realized by the following steps: controlling air humidity of a relatively closed electrolytic plant or directly introducing relatively dry air with certain water content into the electrolytic cell, and controlling the water content in the atmosphere in the electrolytic cell to carry out electrolysis under the condition of 0.5-2 vol.%. The method is convenient and simple in process operation, is suitable for quickly and efficiently improving the summer current efficiency in high-temperature and high-humidity areas, and can improve the summer current efficiency by more than 15%.
Description
Technical Field
The invention belongs to the technical field of fused salt electrolysis, and particularly relates to a method for improving the lithium metal electrolysis current efficiency in summer in a high-temperature and high-humidity area.
Background
The molten salt electrolysis of metallic lithium is currently in industryThe main means for producing metallic lithium. The metal lithium electrolysis in high-temperature and high-humidity areas has low current efficiency in summer. The average environmental temperature in summer is 26-36 deg.C, the highest temperature in workshop is 50 deg.C, relative humidity is 20-30%, and absolute humidity of air is 15g/m3-25g/m3The volume ratio of water vapor in the air is 2-3 vol%, and the current efficiency is 50-60%; the environmental temperature in winter is 5-25 ℃, the highest temperature in a workshop can reach 30 ℃, the relative humidity is 7-20 percent, and the absolute humidity in the air is 6g/m3-15g/m3The volume ratio of water vapor in the air is 0.8 vol.% to 2 vol.%, the current efficiency is 80% to 90%, and the method is much higher than summer.
The present invention improves current efficiency by reducing the water content in the ambient air or in the tank atmosphere.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to solve the problem of low summer current efficiency in a high-temperature high-humidity area in the prior art, and provides a process for improving the summer current efficiency in the high-temperature high-humidity area so as to overcome the defects of the prior art.
The purpose of the invention is realized by the following technical scheme:
the method comprises the following steps: the module type air-cooled water chilling unit is used for providing 20-25 ℃ of temperature and 0.2g/m of absolute humidity3-1g/m3Low humidity air.
The modular air-cooled water chilling unit is equivalent to an industrial air conditioner, air with required conditions is provided by the equipment, and the obtained air is led to the surface of the electrolytic bath through the vent hole, so that the air humidity in the electrolytic environment is changed.
Step two: an operation room is arranged outside the electrolytic cell, a hygrothermograph is respectively arranged inside and outside the workshop, and the temperature and humidity data in the working environment of the electrolytic cell are monitored and recorded at any time.
The operation room is a closed space formed by directly building a partition plate outside the electrolysis device, and the function of the operation room is to reduce the leakage of low-humidity air provided by the modular air-cooled water chilling unit and reduce the influence of the environment on the method.
The humiture meter is an auxiliary detection means and can be directly placed in an operation room.
Step three: and (3) introducing the low-humidity air obtained in the step one into an operation workshop or the surface of the electrolytic bath, and controlling the water vapor volume ratio to be between 0.5 and 2 vol.%, preferably between 0.8 and 1.5 vol.% through reading and recording by a hygrothermograph.
The control method is to calculate the water vapor content in the air by reading the reading of the hygrothermograph. When the water vapor content is higher, the air quantity of the modular air-cooled water chilling unit can be increased to reduce the humidity; the air quantity is reduced when the water vapor content is lower.
Step four: and collecting the metal lithium product every 2 hours, sampling and calculating the current efficiency, and simultaneously recording the temperature and humidity data in the environment of the electrolysis process.
The collecting operation of the lithium metal product is to utilize a porous leakage net and open the cover of the electrolytic cell to directly fish the liquid lithium metal in the electrolytic cell within the electrolysis temperature range of 400-500 ℃.
The current efficiency calculation method comprises the steps of weighing the obtained metal lithium after fishing, and determining the ratio of the obtained metal lithium to the theoretical metal lithium yield within a period of time as the current efficiency.
The process of the invention relating to the electrolysis of metallic lithium comprises the following steps: pouring a certain proportion of LiCl-KCl (preferably LiCl: KCl: 45 wt.%: 55 wt.% -50 wt.%: 50 wt.%) mixed raw materials into an electrolytic cell, introducing alternating current to heat the mixed raw materials to 400-450 ℃ to melt the raw materials, introducing 10KA-100KA direct current to electrolyze the mixed raw materials, opening a cover of the electrolytic cell after electrolyzing for a certain time (preferably 2-8h), directly fishing out lithium metal, weighing the lithium metal, and calculating the current efficiency.
Compared with the prior art, the invention has the following positive effects:
the process is convenient and simple to operate, is suitable for industrial application, and is a method for quickly and efficiently improving and stabilizing the summer current efficiency in high-temperature and high-humidity areas, and the summer current efficiency can be improved by more than 15%. The current efficiency of the current industrial production is about 65%, and the current efficiency can reach about 90% by increasing the operation (introducing air with certain humidity to the surface of the electrolytic cell).
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The lithium metal electrolysis process in the following examples was:
pouring 50 wt.% LiCl-KCl mixed raw material into an electrolytic cell, introducing alternating current, heating to 400-450 ℃, melting the raw material to a molten state, introducing 25KA direct current for electrolysis, opening a cover of the electrolytic cell after 4 hours of electrolysis, directly fishing out lithium metal, and weighing to calculate current efficiency.
Example 1
The method comprises the following steps: the modular air-cooled water chilling unit is utilized to provide 25 ℃ of absolute humidity of 1.0g/m3Low humidity air of (2);
step two: an operation room is arranged outside the electrolytic cell, a hygrothermograph is respectively arranged inside and outside the workshop, and the temperature and humidity data in the working environment of the electrolytic cell are monitored and recorded at any time
Step three: introducing the low-humidity air obtained in the step one into an operation workshop, reading and recording through a hygrothermograph, and controlling the volume ratio of water vapor to be 1.5 vol%;
step four: and collecting the metal lithium product every 2 hours, sampling and calculating the current efficiency, and simultaneously recording the temperature and humidity data in the environment of the electrolysis process.
The current efficiency reaches 90 percent.
Calculating the current efficiency: the theoretical yield of electrolytic lithium metal is (0.26 is the electrochemical equivalent constant of lithium, in g/a × h):
Wtheory of the invention＝0.26*I*t
＝0.26*25000*4
＝26kg
Weighing to obtain actual yield W of lithium by fishing out lithium metalPractice ofThe current efficiency was obtained at 23.4 kg:
η＝Wpractice of/WTheory of the invention×100％
＝23.4/26×100％
＝90％
Example 2
The method comprises the following steps: the module type air-cooled water chilling unit is used for providing 20 ℃ and the absolute humidity is 0.2g/m3Low humidity air of (2);
step two: the thermo-hygrometers are respectively arranged inside and outside the operation workshop, and the temperature and humidity data in the working environment of the electrolytic cell are monitored and recorded at any time
Step three: directly introducing the low-humidity air obtained in the step one to the surface of the electrolytic cell, reading and recording through a hygrothermograph, and controlling the volume ratio of water vapor to be 0.8 vol%;
step four: and collecting the metal lithium product every 2 hours, sampling and calculating the current efficiency, and simultaneously recording the temperature and humidity data in the environment of the electrolysis process.
The current efficiency reaches 90 percent.
The current efficiency calculation process is the same as above.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (5)
1. A method for increasing the current efficiency of lithium metal electrolysis, comprising the steps of: the module type air-cooled water chilling unit is used for providing 20-25 ℃ of temperature and 0.2g/m of absolute humidity3-1g/m3Low humidity air of (2); arranging an operation room outside the electrolytic cell, respectively arranging a hygrothermograph inside and outside the workshop, and monitoring and recording temperature and humidity data in the working environment of the electrolytic cell at any time; introducing low-humidity air into operation workshop or electrolytic cell, and controlling absolute humidity at 6g/m3-15g/m3Within the range; and collecting the metal lithium product every 2 hours, sampling and calculating the current efficiency, and simultaneously recording the temperature and humidity data in the environment of the electrolysis process.
2. The method for improving the current efficiency of lithium metal electrolysis according to claim 1, wherein the water vapor content in the atmosphere is controlled by directly introducing air with low humidity of 20 ℃ to 25 ℃ into the electrolysis workshop or the surface of the electrolytic cell.
3. The method of claim 1, wherein the absolute humidity of the atmosphere in the cell is controlled to 6g/m3-15g/m3In the range of 0.5 vol.% to 2 vol.% of water vapour content.
4. A method for increasing the current efficiency of lithium metal electrolysis according to claim 3 wherein the water vapour content of the atmosphere in the cell is controlled to be in the range of 0.8 vol.% to 1.5 vol.%.
5. The method of claim 1, wherein the operating room forms a closed space for installing a partition outside the electrolyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010886397.4A CN112064063A (en) | 2020-08-28 | 2020-08-28 | Method for improving current efficiency of metal lithium electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010886397.4A CN112064063A (en) | 2020-08-28 | 2020-08-28 | Method for improving current efficiency of metal lithium electrolysis |
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| Publication Number | Publication Date |
|---|---|
| CN112064063A true CN112064063A (en) | 2020-12-11 |
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| CN202010886397.4A Pending CN112064063A (en) | 2020-08-28 | 2020-08-28 | Method for improving current efficiency of metal lithium electrolysis |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4276145A (en) * | 1980-01-31 | 1981-06-30 | Skala Stephen F | Electrolytic anolyte dehydration of castner cells |
| US5285960A (en) * | 1992-11-10 | 1994-02-15 | Gas Research Institute | Lithium chloride humidistat |
| JP2019059971A (en) * | 2017-09-25 | 2019-04-18 | 東邦チタニウム株式会社 | Drying method of molten salt electrolytic bath |
| JP2020002403A (en) * | 2018-06-26 | 2020-01-09 | 東邦チタニウム株式会社 | Moisture reduction method for molten salt, molten salt electrolysis method, and production method of molten metal |
-
2020
- 2020-08-28 CN CN202010886397.4A patent/CN112064063A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4276145A (en) * | 1980-01-31 | 1981-06-30 | Skala Stephen F | Electrolytic anolyte dehydration of castner cells |
| US5285960A (en) * | 1992-11-10 | 1994-02-15 | Gas Research Institute | Lithium chloride humidistat |
| JP2019059971A (en) * | 2017-09-25 | 2019-04-18 | 東邦チタニウム株式会社 | Drying method of molten salt electrolytic bath |
| JP2020002403A (en) * | 2018-06-26 | 2020-01-09 | 東邦チタニウム株式会社 | Moisture reduction method for molten salt, molten salt electrolysis method, and production method of molten metal |
Non-Patent Citations (2)
| Title |
|---|
| 张松岩 等: "工艺条件对金属锂电解过程影响研究" * |
| 张松岩 等: "水分对金属锂电解电流效率影响及其机理探究" * |
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Application publication date: 20201211 |