CN114464953A - Pre-sodium treatment method of diaphragm for sodium ion battery - Google Patents
Pre-sodium treatment method of diaphragm for sodium ion battery Download PDFInfo
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- CN114464953A CN114464953A CN202111615874.4A CN202111615874A CN114464953A CN 114464953 A CN114464953 A CN 114464953A CN 202111615874 A CN202111615874 A CN 202111615874A CN 114464953 A CN114464953 A CN 114464953A
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- sodium
- diaphragm
- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
Abstract
The invention discloses a pre-sodium treatment method of a diaphragm for a sodium ion battery, which comprises the following steps: (1) adding metal sodium into a heating kettle under the protection of inert gas, heating to 97-150 ℃ to heat and melt the metal sodium to obtain metal sodium melt; (2) uniformly coating molten sodium on a diaphragm through a coating device in a vacuum or argon environment; (3) cooling the diaphragm coated with the metal sodium by a cooling roller in a vacuum drying environment or under the protection of argon, wherein the temperature of the cooling roller is set to be 30-70 ℃; (4) rolling the cooled diaphragm by a roller press, wherein the gap range of the roller press is 5-100 mu m, and the pressure is 2-100 tons; (5) and rolling the rolled diaphragm with the sodium layer, and assembling the diaphragm serving as a sodium-ion battery for later use. The pre-sodium treatment method provided by the invention can effectively improve the first-cycle coulombic efficiency and gram-capacity exertion of the sodium-ion battery, is simple and feasible, and can adjust the thickness of a coated sodium layer according to requirements. The invention has the advantages of rapid production, low cost and convenient operation.
Description
Technical Field
The invention relates to a pre-sodium treatment method of a diaphragm for a sodium ion battery, belonging to the technical field of sodium ion batteries.
Background
The sodium ion battery has the outstanding advantages of rich resources, low price, wide distribution and the like, thereby arousing the wide attention of people and being expected to become a substitute of the lithium ion battery. In recent years, research on sodium ion batteries has achieved certain results, and research systems have also been perfected. The sodium ion energy density (typically 120Wh/kg) is significantly lower than that of lithium iron phosphate batteries (160Wh/kg) and ternary batteries, and the lower energy density also limits their commercial applications.
The negative electrode materials of the currently reported sodium ion batteries suitable for commercialization are all hard carbon, and similar to the lithium ion batteries, in the first-cycle charge and discharge process of the sodium ion batteries, part of sodium can be consumed at the negative electrode side to form an SEI film, which has great influence on the specific energy of the batteries and the long-life cycle in the later period. On the premise that a battery material system has no major breakthrough, the energy density and the cycle performance of the sodium-ion battery are improved and the industrialization of the sodium-ion battery is promoted by pre-sodium treatment at present.
The early pre-sodium treatment method is to assemble a battery pole piece and sodium metal into a half battery, pre-treat a pole piece by an electrochemical sodium embedding method, and then use the pre-sodium treated pole piece for the assembly of a full battery, but the treatment cost is higher, the price is expensive, and the method is not suitable for continuous production.
Another method of pre-sodium modification is by sodium supplement additives. Such as sodium azide (NaN)3) Sodium phosphide (Na)3P), sodium peroxide (Na)2O2) Sodium nickelate (NaNiO)2) Sodium carbonate (Na)2CO3) Sodium oxalate (Na)2C2O4) And the like. However, they all have certain disadvantages in terms of industrialization, such as NaN3、Na3P is extremely toxic and explosive; NaNiO2The capacity release efficiency is not high, the capacity can not be obviously improved, and the contained heavy metal also causes pollution to the environment.
Therefore, it is of great significance to develop a pre-sodium treatment method which is simple and easy to implement and easy to be applied in industrialization.
Disclosure of Invention
The invention aims to provide a pre-sodium treatment method of a diaphragm for a sodium ion battery, which can effectively improve the first-week coulombic efficiency and gram capacity exertion of the sodium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a pre-sodium treatment method of a diaphragm for a sodium ion battery comprises the following steps:
(1) adding metal sodium into a heating kettle under the protection of inert gas, heating to above 98 ℃ to heat and melt the metal sodium to obtain a metal sodium melt;
(2) uniformly coating molten sodium on a diaphragm through a coating device in a vacuum or argon environment;
(3) cooling the diaphragm coated with the metal sodium by a cooling roller in a vacuum drying environment or under the protection of argon, wherein the temperature of the cooling roller is set to be 30-70 ℃;
(4) rolling the cooled diaphragm by a roller press under the pressure of 2-100 tons;
(5) and rolling the rolled diaphragm with the sodium layer, and assembling the diaphragm serving as a sodium ion battery for later use.
Preferably, in the step (1), the lining of the heating kettle is made of ceramic or polytetrafluoroethylene material, and the inert gas is nitrogen or argon.
Preferably, the surface of the membrane has a glue layer, which is a polymer binder, such as polyvinylidene fluoride (PVDF). The diaphragm is made of one of PE (polyethylene), PP (polypropylene) and PP/PE/PP (multilayer composite material).
Preferably, in the step (2), the diaphragm is dried in vacuum at 85 ℃ for 24 hours in advance, and the coating mode can be a transfer mode, a squeezing mode or an immersion mode.
Preferably, in the step (2), the inner surface of the fluid mold of the coating device is provided with a heat insulation layer, and the gap of the die head of the coating device is adjustable, wherein the gap ranges from 5 micrometers to 100 micrometers.
Preferably, in the step (3), the surface of the cooling roller is provided with a protective layer, and the material of the protective layer is polytetrafluoroethylene, ceramic, organic silicon polymer, and the like.
Preferably, in the step (4), the main function of the rolling is to perform a shaping-like function on the sodium coating layer, and the surface of the rolling machine is provided with a protective layer made of polytetrafluoroethylene, ceramic, organic silicon polymer and the like. The roll gap range of the roll squeezer is 5-100 mu m, and in the rolling process, the roll gap range of the roll squeezer is controlled to be 1-2 mu m smaller than the thickness of the diaphragm coated with sodium
The invention has the beneficial effects that:
the pre-sodium treatment method provided by the invention can effectively improve the first-week coulombic efficiency and gram-capacity exertion of the sodium ion battery, is simple and feasible, and can adjust the thickness of a coated sodium layer, namely the pre-sodium amount according to requirements. The invention has the advantages of rapid production, low cost and convenient operation.
Drawings
Fig. 1 is a schematic flow chart of a method for pre-sodium treatment of a separator for a sodium ion battery according to the present invention.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a schematic flow diagram of the pre-sodium treatment method of the present invention. The method comprises the following steps: heating and melting metal sodium in a heating kettle to prepare a metal sodium melt; coating molten sodium on the diaphragm by a coating mode; the coating mode can be a transfer mode, an extrusion mode or an immersion mode; and after coating, cooling the diaphragm with the metal sodium melt coating by a cooling roller in a vacuum drying environment or under the protection of argon, rolling the diaphragm with the metal sodium layer, and finally rolling.
As a specific example of the invention, a separator with a metallic sodium layer having a thickness of about 15 μm was prepared, with a specific pre-sodium treatment process:
and adding metal sodium into a heating kettle under the protection of argon, and heating to 99 ℃ to completely melt the metal sodium to obtain a metal sodium melt. Uniformly coating molten metal sodium on a diaphragm by a coating device in a transfer coating mode in an argon environment, wherein the diaphragm is made of PE (polyethylene) and is provided with a polyvinylidene fluoride glue layer on the surface, and the diaphragm is dried in vacuum at 85 ℃ for 24 hours in advance; the inner surface of a fluid die of the used coating device is provided with a heat-insulating layer, and the gap of a die head of the coating device is adjustable, wherein the gap range is 25 mu m. And (3) cooling the diaphragm coated with the metal sodium by a cooling roller under the protection of argon, wherein the surface of the cooling roller is provided with a polytetrafluoroethylene protective layer, and the temperature is set to be 30 ℃. And rolling the cooled diaphragm by a roller press, wherein the surface of the roller press is provided with a polytetrafluoroethylene protective layer, the gap range is 23 mu m, and the pressure is 50 tons, so that the diaphragm with the thickness of a sodium layer of 15 mu m is obtained. And rolling the rolled diaphragm with the sodium layer, and assembling the diaphragm serving as a sodium ion battery for later use.
In the following examples, the sodium ion battery was manufactured into a cell according to the conventional manufacturing process of the sodium ion battery. The sodium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm with a sodium layer and electrolyte. Wherein the positive electrode can be transition metal oxide (Na)xMO2Type positive electrode, etc.), polyanion type compound (olivine type naffepo)4NASICON type Na3V2(PO4)3Fluorophosphate, pyrophosphate, sulfate), prussian blue-based compounds, and the like. The negative electrode is hard carbon. NaPF at 1M6And the electrolyte is prepared from the following components of/EC + DEC + FEC (the volume ratio is 10:10: 1).
Example 1
Hard carbon is used as a positive electrode, and metal sodium is used as a negative electrode; assembling a button half-cell using the membrane obtained above with a sodium layer having a thickness of 15 μm; charging and discharging at 0.05C for 3 weeks, and voltage interval of 0.005-2V. The gram capacity exertion (first-week discharge capacity of the battery divided by the mass of the positive electrode active material) and first-week coulombic efficiency of the sodium ion battery were measured, and the results are shown in table 1.
Example 2
Using Na0.67Fe0.5Mn0.5O2As the positive electrode, hard carbon as the negative electrode; a full cell was assembled using the separator having a sodium layer with a thickness of 15 μm obtained above; charging and discharging at 0.1C for 3 weeks, and voltage interval of 1.0-4.1V. The gram capacity exertion and first week coulombic efficiency of the sodium ion battery were measured, and the results are shown in table 1.
Comparative example 1
Hard carbon is used as a positive electrode, and metal sodium is used as a negative electrode; assembling a button half cell by using a common PE diaphragm; charging and discharging at 0.05C for 3 weeks, and voltage interval of 0.005-2V. The gram capacity exertion and first week coulombic efficiency of the sodium ion battery were measured, and the results are shown in table 1.
Comparative example 2
Using Na0.67Fe0.5Mn0.5O2As the positive electrode, hard carbon as the negative electrode;
assembling a full cell by using a common PE diaphragm as a diaphragm;
charging and discharging at 0.1C for 3 weeks, and voltage interval of 1.0-4.1V. The gram capacity exertion and first week coulombic efficiency of the sodium ion battery were measured, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the first coulombic efficiency and gram capacity exertion of the sodium-ion battery can be effectively improved by adopting the technology provided by the invention.
The above-mentioned embodiments only represent several embodiments of the present invention, but it should be understood by those skilled in the art that these are only examples, and other corresponding changes and modifications can be made according to the above-mentioned technical solutions and concepts, which fall into the protection scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A pre-sodium treatment method of a diaphragm for a sodium ion battery is characterized by comprising the following steps:
(1) adding metal sodium into a heating kettle under the protection of inert gas, heating to 97-150 ℃ to heat and melt the metal sodium to obtain metal sodium melt;
(2) uniformly coating molten sodium on a diaphragm through a coating device in a vacuum or argon environment;
(3) cooling the diaphragm coated with the metallic sodium by a cooling roller in a vacuum drying environment or under the protection of argon, wherein the temperature of the cooling roller is set to be 30-70 ℃;
(4) rolling the cooled diaphragm by a roller press, wherein the gap range of the roller press is 5-100 mu m, and the pressure is 2-100 tons;
(5) and rolling the rolled diaphragm with the sodium layer, and assembling the diaphragm serving as a sodium ion battery for later use.
2. The method for pre-sodium treatment of the diaphragm for the sodium-ion battery as claimed in claim 1, wherein in the step (1), the lining of the heating kettle is made of ceramic or polytetrafluoroethylene material, and the inert gas is nitrogen or argon.
3. The method for pre-sodium treatment of a separator for a sodium ion battery as claimed in claim 1, wherein the surface of the separator has a glue layer, and the glue layer is a polymer binder.
4. The method for pre-sodium treatment of a separator for a sodium-ion battery according to claim 1, wherein the material of the separator is one of PE, PP and PP/PE/PP.
5. The method for pre-sodium treatment of the separator for the sodium-ion battery according to claim 1, wherein in the step (2), the separator is dried in vacuum at 85 ℃ for 24 hours in advance, and the coating mode is a transfer mode, a squeezing mode or an immersion mode.
6. The method for pre-sodium treatment of the separator for the sodium-ion battery according to claim 1, wherein in the step (2), the inner surface of the fluid mold of the coating device is provided with the heat-insulating layer, and the gap of the die head of the coating device is adjustable, wherein the gap ranges from 5 μm to 100 μm.
7. The method for pre-sodium treatment of a separator for a sodium ion battery according to claim 1, wherein in the step (3), the surface of the cooling roll is provided with a protective layer made of polytetrafluoroethylene, ceramic or organic silicon polymer.
8. The method for pre-sodium treatment of the separator for sodium ion battery as claimed in claim 1, wherein in the step (4), the surface of the roller press is provided with a protective layer made of polytetrafluoroethylene, ceramic or organic silicon polymer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115117558A (en) * | 2022-08-01 | 2022-09-27 | 湖南钠方新能源科技有限责任公司 | Sodium supplement composition and sodium ion battery |
| CN115882159A (en) * | 2023-03-08 | 2023-03-31 | 四川中科兴业高新材料有限公司 | Preparation method of sodium battery diaphragm based on PPS |
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| CN110197888A (en) * | 2018-02-26 | 2019-09-03 | 比亚迪股份有限公司 | A kind of battery diaphragm and lithium ion battery |
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| WO2020174496A1 (en) * | 2019-02-28 | 2020-09-03 | Kpit Technologies Limited | A high-power density sodium-ion battery |
| CN112928381A (en) * | 2019-12-06 | 2021-06-08 | 北京航空航天大学 | Lithium-supplementing electrode plate and lithium-supplementing diaphragm of lithium ion battery and preparation method of lithium-supplementing electrode plate and lithium-supplementing diaphragm |
| CN113346192A (en) * | 2021-05-20 | 2021-09-03 | 华中科技大学 | Lithium ion battery composite diaphragm and preparation method and application thereof |
| CN113675533A (en) * | 2021-06-29 | 2021-11-19 | 东莞凯德新能源有限公司 | Composite coating sodium ion battery diaphragm and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115117558A (en) * | 2022-08-01 | 2022-09-27 | 湖南钠方新能源科技有限责任公司 | Sodium supplement composition and sodium ion battery |
| CN115882159A (en) * | 2023-03-08 | 2023-03-31 | 四川中科兴业高新材料有限公司 | Preparation method of sodium battery diaphragm based on PPS |
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