A quasi-solid sodium battery electrolyte, and a preparation method and application thereof
By preparing a quasi-solid sodium electrolyte containing a photocuring agent, a sodium ion electrolyte, and two-dimensional materials, the problems of low ionic conductivity and interfacial resistance of solid electrolytes were solved, and high specific capacity and long cycle stability of sodium metal batteries were achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2023-09-06
- Publication Date
- 2026-07-10
AI Technical Summary
The low ionic conductivity and large interfacial resistance of existing solid electrolytes limit the practical application of sodium metal batteries, and their cycle stability is insufficient.
A quasi-solid sodium electrolyte is prepared by using a photocuring agent, sodium ion electrolyte, and two-dimensional materials such as fluorinated graphene, titanium nitride, boron nitride, silicon disulfide, tungsten disulfide, or silicon carbide. The electrolyte has good mechanical strength and stability.
This improved the ionic conductivity of sodium metal batteries, reduced resistance, and enabled high specific capacity at both low and high rates, while maintaining long-term cycle stability.
Smart Images
Figure CN119581652B_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of sodium metal battery technology, and particularly relates to a quasi-solid-state sodium electrolyte, its preparation method and application. Background Technology
[0002] Solid electrolytes can address the safety issues associated with traditional organic liquid electrolytes. However, their low ionic conductivity and high interfacial resistance limit their practical applications. Therefore, improving the ionic conductivity and reducing the interfacial resistance of solid electrolytes are crucial for developing high-performance sodium metal batteries.
[0003] Currently, the design and fabrication of quasi-solid-state electrolytes have been reported in the literature. For example, Wen Pengchao et al. (Adv. Energy Mater. 2021, 11, 2002930) successfully prepared a photopolymerizable gel electrolyte with high room-temperature ionic conductivity, suitable for high-energy-density solid sodium metal batteries; however, its specific capacity at high rates is relatively low. Wei Ling et al. (Adv. Energy Mater. 2020, 10, 1903966) successfully prepared a multilayer flexible solid electrolyte for sodium metal batteries. The multilayer flexible solid electrolyte shows great advantages in solving the problems of ionic conductivity and interfacial resistance; however, the sodium metal solid-state battery composed of this electrolyte cannot maintain long-term cycle stability. Summary of the Invention
[0004] To address the aforementioned technical problems, this application provides a quasi-solid sodium electrolyte, its preparation method, and its application. The quasi-solid sodium electrolyte exhibits good mechanical strength and stability, reduces resistance, and improves ionic conductivity. When applied to sodium metal batteries, the quasi-solid sodium electrolyte demonstrates high specific capacity at both low and high rates and maintains long-term cycle stability.
[0005] To achieve the above-mentioned objectives, this application provides the following technical solution:
[0006] On the one hand, this application provides a quasi-solid sodium electrolyte, which includes a photocuring agent, a sodium ion electrolyte, and a two-dimensional material;
[0007] The two-dimensional material includes one or more of fluorinated graphene, titanium nitride, boron nitride, silicon disulfide, tungsten disulfide, and silicon carbide.
[0008] Optionally, the sodium ion electrolyte includes sodium perchlorate, propylene carbonate, and fluoroethylene carbonate.
[0009] Optionally, the volume ratio of the sodium ion electrolyte to the photocuring agent is 3~5:1, wherein the volume of the sodium ion electrolyte is based on the volume of the substance itself, and the volume of the photocuring agent is based on the volume of the substance itself.
[0010] Optionally, the mass ratio of the two-dimensional material to the photocuring agent is 0.1% to 20%, wherein the mass of the two-dimensional material is based on the mass of the material itself, and the mass of the photocuring agent is based on the mass of the material itself.
[0011] Secondly, this application provides a method for preparing the aforementioned quasi-solid sodium electrolyte, comprising the following steps:
[0012] The photocuring agent, sodium ion electrolyte, and two-dimensional material are mixed and cured to obtain the quasi-solid sodium electrolyte.
[0013] Optionally, the volume ratio of the sodium ion electrolyte to the photocuring agent is 3~5:1, wherein the volume of the sodium ion electrolyte is based on the volume of the substance itself, and the volume of the photocuring agent is based on the volume of the substance itself.
[0014] Optionally, the mass ratio of the two-dimensional material to the photocuring agent is 0.1% to 20%, wherein the mass of the two-dimensional material is based on the mass of the material itself, and the mass of the photocuring agent is based on the mass of the material itself.
[0015] Optionally, the photocuring agent includes a photocuring monomer and a photoinitiator.
[0016] Optionally, the mass ratio of the photocurable monomer to the photoinitiator is 90~110:1, wherein the mass of the photocurable monomer is based on the mass of the substance itself, and the mass of the photoinitiator is based on the mass of the substance itself.
[0017] Optionally, the photocurable monomer includes ethoxylated trimethylolpropane triacrylate;
[0018] The photoinitiator includes 2-hydroxy-2-methylphenylacetone.
[0019] Optionally, the sodium ion electrolyte includes sodium perchlorate, propylene carbonate, and fluoroethylene carbonate.
[0020] Optionally, the two-dimensional material includes one or more of fluorinated graphene, titanium nitride, boron nitride, silicon disulfide, tungsten disulfide, and silicon carbide.
[0021] Optionally, the mass ratio of sodium perchlorate, propylene carbonate, and fluoroethylene carbonate is 50~100:1~5:1~5.
[0022] Optionally, the curing is performed using an ultraviolet lamp.
[0023] Optionally, the wavelength of the ultraviolet lamp is 350~450nm.
[0024] Optionally, the curing time is 20~60s.
[0025] Thirdly, this application provides the application of the aforementioned quasi-solid-state sodium electrolyte in the preparation of sodium metal batteries.
[0026] Compared with the prior art, this application has the following advantages:
[0027] (1) The quasi-solid sodium electrolyte provided in this application has good mechanical strength and mechanical stability, which can reduce the resistance of the quasi-solid sodium electrolyte and improve the ionic conductivity.
[0028] (2) The quasi-solid sodium electrolyte prepared by the preparation method provided in this application has high quality, good performance and wide range of applications.
[0029] (3) When the quasi-solid sodium electrolyte provided in this application is applied to sodium metal batteries, it has a high specific capacity at both low and high rates and can maintain long-term cycle stability. Attached Figure Description
[0030] Figure 1 EIS testing was performed on the quasi-solid sodium electrolyte prepared in Example 1 of this application;
[0031] Figure 2 Ionic conductivity test of the quasi-solid sodium electrolyte prepared in Example 1 of this application;
[0032] Figure 3 The constant current charge-discharge curve of the quasi-solid-state sodium electrolyte prepared in Example 1 of this application in a sodium metal battery;
[0033] Figure 4 Electroplating / stripping curves of the quasi-solid sodium electrolyte prepared in Example 1 of this application in a sodium-sodium symmetric cell. Detailed Implementation
[0034] The present application is further illustrated below with reference to specific embodiments. The following descriptions are merely a few embodiments of the present application and are not intended to limit the present application in any way. Although the present application discloses preferred embodiments as follows, they are not intended to limit the present application. Any modifications or variations made by those skilled in the art without departing from the scope of the technical solution of the present application using the disclosed technical content are equivalent to equivalent implementation cases and all fall within the scope of the technical solution.
[0035] Unless otherwise specified, the raw materials used in the embodiments of this application are all purchased commercially and used directly without any special treatment.
[0036] Unless otherwise specified, the analytical methods in the embodiments all adopt conventional instrument or equipment settings and conventional analytical methods.
[0037] In the following examples, ETPTA is the photocurable monomer ethoxylated trimethylolpropane triacrylate, and HMPP is the photoinitiator 2-hydroxy-2-methylphenylacetone. + The electrolyte is 1.0M NaClO4 dissolved in propylene carbonate (PC) and 5% fluoroethylene carbonate (FEC) solution, wherein the mass ratio of NaClO4, propylene carbonate (PC) and fluoroethylene carbonate is 100:5:5.
[0038] Example 1
[0039] A method for preparing a quasi-solid-state sodium electrolyte, comprising the following steps:
[0040] Two-dimensional material boron nitride with different contents (the mass ratio of boron nitride to photocuring agent was 0%, 1%, 2.5%, and 5%, respectively) was mixed with 200 μL of photocuring agent (ETPTA:HMPP=100:1) and 800 μL of Na + After the electrolyte is mixed and vibrated evenly, it is cured with 395nm ultraviolet light for 30s to obtain a quasi-solid sodium electrolyte.
[0041] Example 2
[0042] A method for preparing a quasi-solid-state sodium electrolyte, comprising the following steps:
[0043] Two-dimensional material silicon carbide with different contents (the mass ratio of boron nitride to photocuring agent was 0%, 1%, 2.5%, and 5%, respectively) was mixed with 200 μL of photocuring agent (ETPTA:HMPP=100:1) and 800 μL of Na + After the electrolyte is mixed and vibrated evenly, it is cured with 395nm ultraviolet light for 30s to obtain a quasi-solid sodium electrolyte.
[0044] Example 3
[0045] A method for preparing a quasi-solid-state sodium electrolyte, comprising the following steps:
[0046] Two-dimensional materials of titanium nitride with different contents (the mass ratio of boron nitride to photocuring agent was 0%, 1%, 2.5%, and 5%, respectively) were mixed with 200 μL of photocuring agent (ETPTA:HMPP=100:1) and 800 μL of Na + After the electrolyte is mixed and vibrated evenly, it is cured with 395nm ultraviolet light for 30s to obtain a quasi-solid sodium electrolyte.
[0047] Example 4
[0048] A method for preparing a quasi-solid-state sodium electrolyte, comprising the following steps:
[0049] Different amounts of two-dimensional material silicon disulfide (the mass ratio of boron nitride to photocuring agent was 0%, 1%, 2.5%, and 5%, respectively) were taken and mixed with 200 μL of photocuring agent (ETPTA:HMPP=100:1) and 800 μL of Na + After the electrolyte is mixed and vibrated evenly, it is cured with 395nm ultraviolet light for 30s to obtain a quasi-solid sodium electrolyte.
[0050] Experimental Example 1
[0051] Electrochemical tests were performed on the quasi-solid sodium electrolytes prepared in Examples 1 to 4. The test methods included EIS testing, constant current charge-discharge testing, and Na-Na symmetric cell electroplating / stripping testing. The EIS testing and constant current charge-discharge testing were performed using a Chenhua 760E electrochemical workstation.
[0052] Typical test results are as follows Figure 1 As shown, this corresponds to the quasi-solid sodium electrolyte prepared in Example 1. Figure 1 The results show that the resistance of the quasi-solid sodium electrolyte decreases after the addition of the two-dimensional material BN.
[0053] Typical test results are as follows Figure 2 As shown, this corresponds to the quasi-solid sodium electrolyte prepared in Example 1. Figure 2 The results show that the ionic conductivity of the quasi-solid sodium electrolyte increases after the addition of the two-dimensional material BN.
[0054] Typical test results are as follows Figure 3 As shown, this corresponds to the quasi-solid sodium electrolyte prepared in Example 1. Figure 3 The results show that sodium metal batteries, after the addition of BN (taking the addition of 1% two-dimensional material boron nitride in Example 1 as an example), have a high specific capacity at high rates.
[0055] Typical test results are as follows Figure 4 As shown, the test results of the quasi-solid sodium electrolyte prepared in Example 1 (taking the addition of 1% two-dimensional material boron nitride in Example 1 as an example) in the electroplating and stripping process of Na-Na symmetric cells show that the electrolyte has good applicability in sodium-sodium symmetric cells.
[0056] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A quasi-solid-state sodium electrolyte, characterized in that, The quasi-solid sodium electrolyte comprises a photocuring agent, a sodium ion electrolyte, and a two-dimensional material; The two-dimensional material includes boron nitride, and the mass ratio of the two-dimensional material to the photocuring agent is 1-5%. The sodium ion electrolyte comprises sodium perchlorate, propylene carbonate and fluoroethylene carbonate, wherein the mass ratio of sodium perchlorate, propylene carbonate and fluoroethylene carbonate is 50~100:1~5:1~5. The photocuring agent includes a photocuring monomer and a photoinitiator, wherein the photocuring monomer is ethoxylated trimethylolpropane triacrylate and the photoinitiator is 2-hydroxy-2-methylphenylacetone.
2. The quasi-solid-state sodium electrolyte according to claim 1, characterized in that, The volume ratio of the sodium ion electrolyte to the photocuring agent is 3~5:1, wherein the volume of the sodium ion electrolyte is based on the volume of the substance itself, and the volume of the photocuring agent is based on the volume of the substance itself.
3. The method for preparing the quasi-solid sodium electrolyte according to any one of claims 1 to 2, characterized in that, Includes the following steps: The photocuring agent, sodium ion electrolyte, and two-dimensional material are mixed and cured to obtain the quasi-solid sodium electrolyte.
4. The method for preparing the quasi-solid sodium electrolyte according to claim 3, characterized in that, The mass ratio of the photocurable monomer to the photoinitiator is 90~110:1, wherein the mass of the photocurable monomer is based on the mass of the substance itself, and the mass of the photoinitiator is based on the mass of the substance itself.
5. The method for preparing the quasi-solid sodium electrolyte according to claim 3, characterized in that, The curing process is performed using an ultraviolet lamp.
6. The method for preparing the quasi-solid sodium electrolyte according to claim 5, characterized in that, The wavelength of the ultraviolet lamp is 350~450nm.
7. The method for preparing the quasi-solid sodium electrolyte according to claim 5, characterized in that, The curing time is 20~60s.
8. The application of the quasi-solid-state sodium electrolyte according to any one of claims 1 to 2 or the quasi-solid-state sodium electrolyte prepared by the preparation method according to any one of claims 3 to 7 in the preparation of sodium metal batteries.