CN107895767B - High-performance composite diaphragm for lithium-sulfur battery and preparation method thereof - Google Patents
High-performance composite diaphragm for lithium-sulfur battery and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a high-performance composite diaphragm for a lithium-sulfur battery and a preparation method thereof, wherein the high-performance diaphragm is used for solving the problems of electronic conductivity, ionic conductivity, cycling stability and the like, a magnetron sputtering double-target co-sputtering technology is used for depositing carbon materials and lanthanum lithium zirconate on a commercial diaphragm, and the method effectively avoids the problems of diaphragm pore blocking and the like caused by a direct coating method, so that the lithium ion conductivity is improved.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a high-performance lithium-sulfur battery composite diaphragm and a preparation method thereof.
Background
The elemental sulfur is used as the anode material, has the highest theoretical specific capacity (1675 m Ah/g) and theoretical specific energy (2600 Wh/kg), and is L iCoO in the traditional lithium ion battery2(274 mAh/g) and the like, and 6 times of the positive electrode material. In addition, the sulfur has huge reserves in the nature, low toxicity and little pollution to the environment. Therefore, lithium-sulfur batteries have become a hot spot of current international research and are ideal choices for new energy power batteries in the future.
However, the true commercialization of lithium sulfur secondary batteries still faces many challenges, and the diffusion of polysulfides and the insulating nature of sulfur are key factors limiting the development of lithium sulfur batteries. First lithium sulfur electricityDuring the charging and discharging process of the battery, the generated higher-valence polysulfide ions which are soluble in the electrolyte can diffuse to the lithium cathode and directly generate side reaction with the metal lithium to generate low-valence lithium polysulfides, and the low-valence lithium polysulfides diffuse back to the sulfur anode to generate high-valence lithium polysulfides, so that a flying shuttle effect is generated, the reduction of the sulfur utilization rate and the corrosion of the lithium cathode are directly caused, the capacity of the battery is rapidly attenuated, the coulombic efficiency is reduced, in addition, the electrical conductivity of S is extremely low (omega =5 × 10-30S/cm at 25 ℃), and insoluble L i is generated in the charging and discharging process2S is deposited on the negative electrode, dendrite is generated on the lithium negative electrode, and the S positive electrode is subjected to volume expansion and fragmentation (76%), which can cause poor cycle stability of the lithium-sulfur battery.
In order to solve the above problems of the lithium sulfur battery, researchers have conducted 5 research works on modification of a positive electrode material, modification of a separator, electrolyte, protection technology of a negative electrode, and structural design of the battery. Among them, the conventional polyolefin separator cannot well inhibit the diffusion of polysulfide, an intermediate product of the lithium sulfur battery, due to the complexity of the charge-discharge reaction process and the diversity of the electrolyte of the lithium sulfur battery. Therefore, the development of higher performance separator materials is also one of the important directions for improving the overall performance of lithium-sulfur batteries.
Yao et al reported that a polymer separator was coated with a layer of different types of conductive carbon to improve the cycling performance of a lithium sulfur battery. Research results show that the conductive carbon layer has better barrier effect on polysulfide. The compact conductive carbon layer can hinder the diffusion of polysulfide, and the conductive layer can also be used as a secondary current collector to reuse the bound polysulfide, so that the utilization rate of active substances is improved, and the loss of battery capacity is avoided. In addition to carbon materials, Zhang et Al reported the metal oxide Al2O3According to modification research of the polymer membrane, polysulfide diffusion can be effectively blocked due to chemical interaction between metal oxygen bonds in the oxide and polysulfide.
The coating modification by adopting the organic carbon material and the inorganic metal oxide has the inhibition effect on polysulfide diffusion to different degrees, however, the surface of the carbon material is nonpolar,it is not possible to form stable chemical bonds with polar polysulfides. Polysulfides are very easily removed from the pores of the carbon material, and it is difficult to effectively inhibit the shuttle effect for a long time. Metal oxides such as TiO2，Al2O3，MnO2For example, the ability to more reliably chemisorb polysulfides is expected to further suppress the shuttling effect of polysulfides. Unfortunately, insulating oxides can impede the transport of electrons and lithium ions, reducing sulfur utilization and rate capability. Good electrical conductivity and reliable chemisorption are difficult to achieve. Therefore, how to mix the two materials uniformly to make up for the weakness and obtain a high-quality lithium-sulfur battery separator is a problem.
In addition, although the direct coating method is adopted to modify the diaphragm, the diffusion of polysulfide can be physically hindered to a certain extent, but the coating can also increase the thickness of the diaphragm, partially block pores, and influence the migration of lithium ions, and the like, namely the barrier rate of polysulfide ions and the passing rate of lithium ions are difficult to achieve a good balance; and the coating unevenness of the diaphragm is high by adopting a direct coating method, so that the lithium ions are unevenly distributed, the growth of lithium dendrites is aggravated, the circulation stability is reduced, and the battery performance is influenced. Therefore, the lithium-sulfur battery separator can effectively inhibit polysulfide diffusion and ensure lithium ion conductivity, and is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a high-performance composite diaphragm for a lithium-sulfur battery and a preparation method thereof, which are used for solving the problems in the conventional lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-performance composite diaphragm for a lithium-sulfur battery is characterized in that a polypropylene diaphragm is used as a base film, and a doped LL ZO/C nano-plating layer is constructed on the surface of the composite diaphragm.
The battery is further characterized in that the doped LL ZO/C nano-plating layer is only arranged towards the positive side of the battery.
The preparation method of the high-performance composite diaphragm for the lithium-sulfur battery is characterized by comprising the following steps of: and (3) adopting a magnetron sputtering double-target co-sputtering technology to perform direct-current sputtering of a pure carbon material and radio-frequency sputtering of lanthanum lithium zirconate on the surface of the polypropylene diaphragm.
The preparation method comprises the following steps:
(1) placing a carbon target, a lanthanum lithium zirconate target and a polypropylene diaphragm into a magnetron sputtering vacuum chamber, vacuumizing to reach a background vacuum degree, and then carrying out magnetron sputtering;
(2) drying the sputtered composite diaphragm in vacuum at 60 ℃ to remove moisture;
(3) and pressing the modified diaphragm into a wafer with the diameter of 18mm by using a manual sheet punching machine to obtain the multifunctional composite diaphragm for the lithium-sulfur battery.
Preferably: the direct current source power of the direct current sputtering is 80W, and the radio frequency source power of the radio frequency sputtering is 30W.
The condition of the magnetron sputtering is that the background vacuum degree is 6.6 × 10-4The sputtering pressure is 0.9Pa, and the sputtering time is 20-40 min.
The invention has the following technical effects:
(1) the doped LL ZO/C nano-plating layer is constructed on the surface of the polypropylene diaphragm, so that the shuttle phenomenon of polysulfide can be effectively inhibited, and the conductivity and the electronic conductivity of lithium ion can be improved.
(2) The doped LL ZO/C nano-coating has high specific surface area of carbon to enable the carbon to physically adsorb polysulfide, and metal oxygen bonds in lanthanum lithium zirconate and the polysulfide have higher binding energy, thereby providing possibility for more reliable chemical adsorption.
(3) The conductivity of carbon makes up the insulation defect of the positive active material sulfur, and the specific structure of the lanthanum lithium zirconate provides a rapid channel for lithium ions. The synergistic effect of the electronically conductive material and the fast ionic conductor material enables the realization of lithium sulfur battery separators with improved lithium ion conductivity and electronic conductivity.
(4) The composite diaphragm of the magnetron sputtering double-target co-sputtering technology has thinner thickness and higher porosity compared with a direct coating method.
(5) The magnetron sputtering technology is convenient to operate, has small influence on the characteristics of the diaphragm, and can be used for large-scale production.
Drawings
FIG. 1 is a schematic structural view of a C/LL ZO/PP composite separator in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the C/LL ZO/PP composite diaphragm in example 1 of the present invention.
FIG. 3 is a diagram of a lithium sulfur battery using a commercial polypropylene separator and showing the structure of the lithium sulfur battery according to example 1, comparative example 1 and comparative example 2 of the present invention
The interfacial impedance of the prepared lithium-sulfur battery is compared with that of the prepared lithium-sulfur battery.
FIG. 4 is a diagram of a lithium sulfur battery using a commercial polypropylene separator and showing the structure of the lithium sulfur battery according to example 1, comparative example 1 and comparative example 2 of the present invention
Lithium ion conductivity of the prepared lithium sulfur battery is compared with that of the prepared lithium sulfur battery.
Fig. 5 is a graph showing the comparison of cycle performance at 0.2C rate of lithium sulfur batteries using a polypropylene commercial separator and modified separators prepared in example 1, comparative example 1, and comparative example 2 of the present invention.
Fig. 6 is a graph comparing rate performance at (0.2C, 0.5C, 1C, 2C, 3C, 0.5C) rate for lithium sulfur batteries using a polypropylene commercial separator and modified separators prepared in example 1, comparative example 1, and comparative example 2 of the present invention.
Detailed Description
Example 1:
a high-performance composite diaphragm for lithium-sulfur battery is composed of commercial polypropylene diaphragm and C and LL ZO nanoparticles sputtered on the surface of basic film, carbon target corresponding to DC source and lanthanum-lithium zirconate target corresponding to RF source, and features that the commercial polypropylene diaphragm is used as substrate, the atmosphere in vacuum chamber is high-purity argon, and the vacuum degree is 6.6 × 10-4Pa, sputtering pressure is controlled to be 0.9Pa, substrate temperature is controlled to be room temperature, direct current sputtering power is 80W, radio frequency sputtering power is 30W, and a sample is depositedThe time interval is 40 min.
Example 2:
a high-performance composite diaphragm for a lithium-sulfur battery comprises a polypropylene commercial diaphragm and C and LL ZO nanoparticles sputtered on the surface of a base film, wherein a carbon target corresponding to a direct current source and a lanthanum lithium zirconate target corresponding to a radio frequency source are well installed, the polypropylene commercial diaphragm is used as a base material, the atmosphere of a vacuum chamber in the sample preparation process is high-purity argon, the background vacuum degree is 6.6 × 10-4 Pa, the sputtering pressure is controlled to be 0.9Pa, the temperature of a substrate is controlled to be room temperature, the direct current sputtering power is 80W, the radio frequency sputtering power is 30W, and the sample deposition time is 30 min.
Example 3:
a high-performance composite diaphragm for lithium-sulfur battery is composed of commercial polypropylene diaphragm and C and LL ZO nanoparticles sputtered on the surface of basic film, carbon target corresponding to DC source and lanthanum-lithium zirconate target corresponding to RF source, and features that the commercial polypropylene diaphragm is used as substrate, the atmosphere in vacuum chamber is high-purity argon, and the vacuum degree is 6.6 × 10-4Pa, controlling the sputtering pressure to be 0.9Pa, controlling the substrate temperature to be room temperature, controlling the direct-current sputtering power to be 80W, controlling the radio-frequency sputtering power to be 30W, and controlling the sample deposition time to be 20 min.
Comparative example 1:
a composite diaphragm of Li-S battery for suppressing the diffusion of polysulfide and increasing the conductivity of positive electrode material is composed of commercial polypropylene diaphragm and nano carbon particles sputtered on the surface of basic film, and features that the target material of pure carbon is installed, the commercial polypropylene diaphragm is used as basic material, the high-purity argon is used as vacuum chamber in sample preparing process, and the vacuum degree is 6.6 × 10-4Pa, controlling the sputtering pressure to be 0.9Pa, controlling the substrate temperature to be room temperature, and sputtering by adopting a direct current source, wherein the sputtering power is 80W, and the sample deposition time is 40 min.
Comparative example 2:
a lithium-sulfur battery composite membrane with high efficiency for inhibiting polysulfide diffusion and improving lithium ion conductivity comprises a polypropylene commercial membrane and lanthanum lithium zirconate nanoparticles sputtered on the surface of a base membrane. The lanthanum lithium zirconate target is well installed, a polypropylene commercial diaphragm is used as a base material, and the sample preparation process is carried outThe atmosphere of the vacuum chamber is high-purity argon, and the background vacuum degree is 6.6 × 10-4Pa, controlling the sputtering pressure to be 0.9Pa, controlling the substrate temperature to be room temperature, sputtering by adopting radio frequency, controlling the sputtering power to be 30W, and controlling the sample deposition time to be 40 min.
Fig. 1 and fig. 2 are a schematic structural diagram of a C/LL ZO/PP composite diaphragm and a scanning electron microscope image respectively in example 1 of the present invention, and as shown in the figure, a modified diaphragm co-sputtered by using C and LL ZO twin targets still retains a part of pore structure, and prevents polysulfide from diffusing while lithium ions pass through.
Fig. 3 is a graph comparing the interfacial impedance of a lithium sulfur battery using a polypropylene commercial separator and the lithium sulfur batteries manufactured according to example 1, comparative example 1 and comparative example 2 of the present invention, and it can be seen that the carbon-modified separator has the lowest interfacial impedance, and the double-sputtered modified separator has similar impedance values, which are both smaller than the commercial separator and the LL ZO single-sputtered modified separator, because the carbon has conductivity, thereby greatly increasing the charge transfer resistance, which is advantageous for increasing the specific capacity of the lithium sulfur battery.
Fig. 4 is a comparative graph of lithium ion conductivity between a lithium-sulfur battery using a polypropylene commercial separator and lithium-sulfur batteries manufactured according to example 1, comparative example 1 and comparative example 2 of the present invention, it can be seen that the LL ZO modified separator has the highest lithium ion conductivity, which is determined by the specific structure of lanthanum lithium zirconate.
Fig. 5 is a graph showing the comparison of cycle performance at 0.2C rate of lithium-sulfur batteries using a polypropylene commercial separator and modified separators according to example 1, comparative example 1 and comparative example 2. it can be seen that the modified separator co-sputtered with C and LL ZO in example 1 has the highest initial specific capacity and the most excellent cycle stability, since uniform mixing of LL ZO and C is achieved by the magnetron sputtering co-sputtering technique, making up for the deficiencies of the former, a high-performance composite separator for lithium-sulfur batteries is achieved.
Fig. 6 is a graph comparing rate performance at (0.2C, 0.5C, 1C, 2C, 3C, 0.5C) current density for lithium sulfur batteries using a polypropylene commercial separator and modified separators prepared according to example 1, comparative example 1, and comparative example 2 of the present invention. As can be seen, the examples all have the highest specific capacities at different current densities.
It should be added that, the sputtering of carbon nano-particles on the commercial diaphragm in the comparative example 1 significantly reduces the charge transfer resistance and physically hinders the diffusion of polysulfide to some extent, but the affinity of non-polar carbon and polar lithium polysulfide is not strong, which results in weak adsorption of polysulfide and is not beneficial to the improvement of cycle stability performance, the sputtering of lanthanum lithium zirconate composite diaphragm in the comparative example 2 improves the lithium ion conductivity and has strong chemical adsorption to polysulfide, but the insulating oxide hinders the electron transmission and reduces the utilization rate of active material.
Claims (6)
1. A composite diaphragm for a lithium-sulfur battery is characterized in that a polypropylene diaphragm is used as a base film, and a doped LL ZO/C nano-coating is constructed on the surface of the composite diaphragm.
2. The composite separator for lithium-sulfur battery according to claim 1, wherein said doped LL ZO/C nano-plating layer is disposed only facing the positive electrode side of the battery.
3. A method for preparing the composite separator for a lithium-sulfur battery according to claim 1 or 2, characterized in that: and (3) adopting a magnetron sputtering double-target co-sputtering technology to perform direct-current sputtering of a pure carbon material and radio-frequency sputtering of lanthanum lithium zirconate on the surface of the polypropylene diaphragm.
4. The method of manufacturing a composite separator for a lithium sulfur battery according to claim 3, characterized by comprising the steps of:
(1) placing a carbon target, a lanthanum lithium zirconate target and a polypropylene diaphragm into a magnetron sputtering vacuum chamber, vacuumizing to reach a background vacuum degree, and then carrying out magnetron sputtering;
(2) drying the sputtered composite diaphragm in vacuum at 60 ℃ to remove moisture;
(3) and pressing the modified diaphragm into a wafer with the diameter of 18mm by using a manual sheet punching machine to obtain the multifunctional composite diaphragm for the lithium-sulfur battery.
5. The method for preparing a composite separator for a lithium-sulfur battery according to claim 4, wherein: the direct current source power of the direct current sputtering is 80W, and the radio frequency source power of the radio frequency sputtering is 30W.
6. The method for preparing the composite diaphragm for the lithium-sulfur battery according to claim 4, wherein the magnetron sputtering is performed under the condition that the background vacuum degree is 6.6 × 10-4The sputtering pressure is 0.9Pa, and the sputtering time is 20-40 min.
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| CN112201904B (en) * | 2020-10-30 | 2023-06-27 | 天目湖先进储能技术研究院有限公司 | Diaphragm intermediate layer material of lithium-sulfur battery, and preparation method and application thereof |
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| CN102407623A (en) * | 2011-08-04 | 2012-04-11 | 中国第一汽车股份有限公司 | Preparation method of composite membrane for lithium ion battery |
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| CN106356488A (en) * | 2015-07-13 | 2017-01-25 | 中国科学院金属研究所 | Composite diaphragm for lithium ion battery for lithium-sulfur battery and preparation method and application of composite diaphragm for lithium ion battery |
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| CN102407623A (en) * | 2011-08-04 | 2012-04-11 | 中国第一汽车股份有限公司 | Preparation method of composite membrane for lithium ion battery |
| CN105990552A (en) * | 2015-02-04 | 2016-10-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Composite diaphragm used for lithium-sulfur battery, preparation method and application thereof |
| CN106356488A (en) * | 2015-07-13 | 2017-01-25 | 中国科学院金属研究所 | Composite diaphragm for lithium ion battery for lithium-sulfur battery and preparation method and application of composite diaphragm for lithium ion battery |
| CN105489892A (en) * | 2016-01-08 | 2016-04-13 | 河南师范大学 | Composite positive electrode plate of lithium-sulfur battery and preparation method of composite positive electrode plate |
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