CN109244330B - Preparation method of high-performance polyolefin composite battery diaphragm and lithium-sulfur battery - Google Patents
Preparation method of high-performance polyolefin composite battery diaphragm and lithium-sulfur battery Download PDFInfo
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- CN109244330B CN109244330B CN201811126107.5A CN201811126107A CN109244330B CN 109244330 B CN109244330 B CN 109244330B CN 201811126107 A CN201811126107 A CN 201811126107A CN 109244330 B CN109244330 B CN 109244330B
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a high-performance polyolefin composite battery diaphragm and a lithium-sulfur battery, belonging to the technical field of methods or devices for converting chemical energy into electric energy, and comprising the following steps of (1) cutting the polyolefin diaphragm into wafers; (2) immersing 5 polyolefin diaphragms into concentrated nitric acid or a mixed solution composed of hydrogen peroxide and potassium peroxodisulfate solution, and continuously stirring for oxidation; (3) mixing ethanol and deionized water according to the volume dosage ratio of 1:1 to form a mixed solvent; (4) adding a transition metal salt into the mixed solvent prepared in the step (3), and continuously stirring to fully dissolve the salt; (5) immersing the diaphragm treated in the step (2) into the transition metal salt solution prepared in the step (4), then dropwise adding hydrogen sulfuric acid, and continuously stirring to graft a transition metal sulfide onto an active site of the diaphragm; (6) and washing and drying to obtain the modified polyolefin diaphragm. The method can obviously improve the surface polarity of the polyolefin diaphragm and the rate capability of the battery.
Description
Technical Field
The invention belongs to the technical field of methods or devices for directly converting chemical energy into electric energy, and particularly relates to a preparation method of a high-performance polyolefin composite battery diaphragm and a lithium-sulfur battery.
Background
The theoretical specific capacity of the lithium-sulfur battery can reach 1675 mAh/g, the energy density can reach 2600Wh/kg, and the lithium-sulfur battery has the advantages of low price, rich sulfur storage, environmental friendliness and the like, and gradually draws wide attention of people. The separator is an indispensable part of a lithium-sulfur battery, and since the polyolefin material has the advantages of low price, good mechanical strength, good chemical stability and the like, and has high-temperature self-closing performance, the safety of the lithium-ion secondary battery in daily use can be ensured, and the microporous separator made of the raw material is widely applied to the lithium-ion battery. In the lithium sulfur battery using the polyolefin separator, a phenomenon in which the negative electrode is corroded during use often occurs, and the cycle performance of the battery is rapidly degraded.
To overcome this problem, Stanford university Stand and others (adv. Mater. 2016, 28, 9797) use Black Phosphorus (BP) to polyene having strong adsorption ability to polar ions such as lithium polysulfide and lithium sulfide and high binding energyThe hydrocarbon diaphragm is modified to prepare the PP-BP composite diaphragm, and the rate capability and the cycle performance of the lithium-sulfur battery are obviously improved. The national center for Nano science, Thangheron et al (adv. Mater. 2017, 29, 1606817) utilize pre-lithiated two-dimensional layered MoS2Modifying a polypropylene diaphragm through MoS on the premise of not increasing the volume and the mass of the diaphragm as much as possible2And polysulfide can be inhibited from moving back and forth due to physical and chemical actions between the polysulfide, so that the shuttle effect of the lithium-sulfur battery is reduced to a certain extent, and the electrochemical performance of the battery is improved. However, the above methods all require the use of a binder, and it is difficult to secure the volumetric energy density and the mass energy density of the battery. In addition, the preparation conditions of the black phosphorus and the prelithiation molybdenum disulfide are harsh, high-temperature and high-pressure conditions are required, and the tert-butyl lithium used in the prelithiation process is flammable and explosive, so that the safety is difficult to guarantee.
Although the research shows that the shuttle effect in the cycle process of the lithium-sulfur battery can be effectively inhibited by modifying a layer of polar nano material with higher binding energy between polysulfide on the surface of the traditional polyolefin diaphragm, the overall performance of the diaphragm is still not ideal, and the key points of reducing the price and simplifying the operation are whether the polyolefin diaphragm can be produced on a large scale or not.
Disclosure of Invention
The invention aims to provide a preparation method of a high-performance polyolefin composite battery diaphragm and a lithium-sulfur battery, which can ensure the energy density of the battery, improve the overall performance of the battery, and have a simple and safe preparation method and are suitable for large-scale production.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method of a high-performance polyolefin composite battery diaphragm is designed, and is characterized by comprising the following steps: the method comprises the following steps:
(1) cutting: cutting the polyolefin diaphragm into circular sheets with the diameter of 19 mm;
(2) and (3) oxidation: immersing 5 pieces of polyolefin diaphragms prepared in the step (1) into concentrated nitric acid or a mixed solution consisting of hydrogen peroxide and potassium peroxodisulfate solution, continuously stirring, and carrying out oxidation treatment on the surfaces of the diaphragms to prepare densely distributed active sites on the surfaces of the diaphragms;
(3) mixing and mixing solvent: mixing ethanol and deionized water into a mixed solvent, wherein the volume usage ratio of the ethanol to the deionized water is 1: 1;
(4) preparing a transition metal salt solution: adding a transition metal salt into the mixed solvent prepared in the step (3), and continuously stirring to fully dissolve the salt;
(5) compounding: immersing the diaphragm treated in the step (2) into the transition metal salt solution prepared in the step (4), then dropwise adding hydrogen sulfuric acid, and continuously stirring to graft a transition metal sulfide onto an active site of the diaphragm;
(6) cleaning and drying: and (5) fishing out the diaphragm processed in the step (5), washing the diaphragm by deionized water for many times, then washing the diaphragm by absolute ethyl alcohol for many times, and then drying the diaphragm in vacuum to obtain the polyolefin diaphragm modified by the transition metal sulfide.
Preferably, in the step (2), 100mL of concentrated nitric acid with the concentration of 98 percent is needed;
the hydrogen peroxide solution is a hydrogen peroxide aqueous solution with the hydrogen peroxide content of 30 percent by mass, the concentration of the potassium peroxodisulfate solution is 0.05M/L, and the mixed solution is prepared by mixing 50mL of hydrogen peroxide and 50mL of potassium peroxodisulfate solution;
the stirring time is 3-3.5 h.
Preferably, the polyolefin membrane in the step (1) is a polyethylene membrane, a polypropylene membrane or a polyethylene and polypropylene composite membrane.
Preferably, in the step (4), 0.5-1.2 g of transition metal salt is added into 100mL of mixed solvent, and the mixture is stirred for 10 min; the transition metal salt is one or the combination of more than two of Ce (SO4)2, FeSO4 & 7H2O, MnSO4 & H2O, (CH3COO)2Cd & 2H2O and NiCl2 & 6H 2O.
Preferably, the concentration of the hydrogen sulfuric acid used in the step (5) is 0.1M/L, the volume is 20-30 mL, the stirring time is 2-2.5 h, and the temperature is room temperature.
Preferably, step (6) is vacuum drying at a temperature of 45 ℃ for 24 h.
The invention also provides a lithium-sulfur battery, which comprises the polyolefin diaphragm and is characterized in that: the polyolefin diaphragm is prepared by the preparation method of the high-performance polyolefin composite battery diaphragm.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the polyolefin diaphragm is modified by adopting the transition metal sulfide, so that the surface polarity of the polyolefin diaphragm can be obviously improved, the wettability and compatibility of the diaphragm to an electrolyte are further improved, the interface compatibility among an electrode, an electrode solution and the diaphragm is improved, the ionic conductivity and ionic migration number of the diaphragm are further improved, the charge transfer resistance of the whole battery system is reduced, and the rate capability of the battery is obviously improved.
2. The diaphragm of the invention can gather polysulfide ions on the surface of the diaphragm from the aspects of physics and chemistry, and prevent the polysulfide ions from diffusing to a negative electrode, and the transition metal sulfide can further activate and utilize the low-conductivity polysulfide ions, thereby improving the actual specific capacity and the cycling stability of a lithium-sulfur battery system.
3. Because the polar transition metal sulfide and polysulfide have higher electron binding energy, the polysulfide can be strongly physically and chemically bound, the back-and-forth migration of the polysulfide in front of a positive electrode and a negative electrode in the battery cycle process is effectively delayed, and the cycle life of the lithium-sulfur battery is remarkably prolonged.
4. The preparation method is simple, efficient and safe, does not need to use a binder, is favorable for ensuring the energy density of the battery and the safety in the production process, and the prepared diaphragm has the capability of relieving the penetration of the lithium dendrite and further improves the safety of the lithium-sulfur battery.
5. The diaphragm of the invention can reduce the cost of raw materials of a lithium-sulfur battery system, has simple and convenient production process and is suitable for large-scale industrial production.
Drawings
Fig. 1 is an SEM image of an unmodified polyethylene separator;
fig. 2 is an SEM image of a cerium sulfide nanoparticle modified polyethylene separator;
FIG. 3 is a graph of rate performance of lithium sulfur batteries assembled with cerium sulfide nanoparticle modified polyethylene separators;
FIG. 4 is a graph of cycling performance at 0.5C for a lithium sulfur battery assembled with an unmodified polyethylene separator;
fig. 5 is a graph of cycle performance at 0.5C for a lithium sulfur battery assembled with a cerium sulfide nanoparticle modified polyethylene separator.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example one
The preparation process of this example is as follows:
(1) cutting: cutting the polyolefin diaphragm into circular sheets with the diameter of 19 mm;
(2) and (3) oxidation: immersing 5 pieces of polyolefin diaphragms prepared in the step (1) into 100 milliliters of concentrated nitric acid with the concentration of 98 percent, stirring for 3 hours, pre-oxidizing the surfaces of the diaphragms, and preparing densely distributed active sites on the surfaces of the diaphragms;
(3) mixing and mixing solvent: mixing ethanol and deionized water into a mixed solvent, wherein the volume usage ratio of the ethanol to the deionized water is 1: 1;
(4) preparing a transition metal salt solution: dissolving 0.5 g of Ce (SO4)2 in 100ml of the mixed solvent prepared in the step (3), and stirring for 10 minutes to completely dissolve;
(5) compounding: immersing the diaphragm treated in the step (2) into the transition metal salt solution prepared in the step (4), then dropwise adding 30ml of hydrosulfuric acid solution with the concentration of 0.1mol/L, and then stirring the solution at room temperature for 2 hours to graft transition metal sulfide onto active sites of the diaphragm;
(6) cleaning and drying: and (4) fishing out the diaphragm processed in the step (5), washing the diaphragm by using deionized water for 3 times, then washing the diaphragm by using absolute ethyl alcohol for 3 times, then placing the diaphragm in a 45-DEG C oven for vacuum drying for 24 hours to obtain the polyethylene diaphragm modified by the cerium sulfide nano particles, and applying the diaphragm to the lithium-sulfur battery.
Example two
The difference between the present embodiment and the first embodiment is:
stirring for 3.5 hours in the step (2) to pre-oxidize the surface of the diaphragm;
in the step (4), 1.2g of FeSO4 & 7H2O is dissolved in 100ml of the mixed solvent prepared in the step (3), and the mixed solvent is stirred for 10 minutes to be completely dissolved
In the step (5), the diaphragm processed in the step (2) is immersed into the transition metal salt solution prepared in the step (4), then 20 ml of hydrogen sulfuric acid solution with the concentration of 0.1mol/L is dropwise added, and then the solution is stirred for 2.5 hours at room temperature;
and (5) obtaining a polypropylene diaphragm modified by ferrous sulfide nano particles in the step (6), and applying the diaphragm to the lithium-sulfur battery.
The rest is the same as the first embodiment.
EXAMPLE III
The difference between the present embodiment and the first embodiment is:
in the step (2), 5 pieces of the polyolefin diaphragm prepared in the step (1) are immersed into 100ml of mixed solution of hydrogen peroxide and potassium peroxodisulfate according to the volume ratio of 1:1, stirred for 3.5 hours, and the surface of the diaphragm is pre-oxidized, wherein the hydrogen peroxide is 15% hydrogen peroxide solution by mass, and the concentration of the potassium peroxodisulfate solution is 0.025 mol/L;
in the step (4), 0.9 g of MnSO 4. H2O is dissolved in 100ml of the mixed solvent prepared in the step (3), and the mixed solvent is stirred for 10 minutes to be completely dissolved;
in the step (5), the diaphragm processed in the step (2) is immersed into the transition metal salt solution prepared in the step (4), then 30ml of hydrogen sulfuric acid solution with the concentration of 0.1mol/L is dropwise added, and then the solution is stirred for 2.5 hours at room temperature;
and (6) obtaining a polyethylene diaphragm modified by manganese sulfide nanoparticles, and applying the diaphragm to the lithium-sulfur battery.
The rest is the same as the first embodiment.
Example four
The difference between the present embodiment and the first embodiment is:
in the step (4), 0.8 g of (CH3COO)2 Cd.2H2O is dissolved in 100ml of the mixed solvent prepared in the step (3), and the mixed solvent is stirred for 10 minutes to be completely dissolved;
in the step (5), the diaphragm processed in the step (2) is immersed into the transition metal salt solution prepared in the step (4), then 30ml of hydrogen sulfuric acid solution with the concentration of 0.1mol/L is dropwise added, and then the solution is stirred for 2 hours at room temperature;
and (6) obtaining a cadmium sulfide nanoparticle modified polyethylene diaphragm, and applying the diaphragm to the lithium-sulfur battery.
The rest is the same as the first embodiment.
The membrane comparison of example one is disclosed herein below: as shown in fig. 1, the through-hole structure of the unmodified Polyethylene (PE) separator can be seen, the void distribution is uniform, and the pore size is about 500 nm. As shown in fig. 2, it can be clearly seen that the surface of the polyethylene separator modified by the cerium sulfide nanoparticles prepared by the present invention is modified by a layer of cerium sulfide nanoparticles, the particles are uniformly distributed on the surface of the separator, and a small amount of the particles are immersed in the gaps of the separator. The rate capability of the lithium-sulfur battery assembled by the separator is shown in figure 3, the specific capacity of 423 mAmp hour/g of the battery is still maintained under the high rate of 3C, and the battery shows excellent rate capability.
The cycle performance of the lithium-sulfur battery assembled by the unmodified polyethylene diaphragm at 0.5 ℃ is shown in fig. 4, the specific capacity of the battery after 400 cycles is only 253 mAmp hour/g, and the capacity retention rate is only 30.1%. The cycle performance of the lithium-sulfur battery assembled by the diaphragm prepared by the invention at 0.5C is shown in figure 5, the specific capacity of the battery after 400 cycles reaches 635 mAmp-hour/g, and the capacity retention rate reaches 72.3%. The performance test results of the other embodiments are equivalent to those of the first embodiment, and are not further described herein.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a high-performance polyolefin composite battery diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) cutting: cutting the polyolefin diaphragm into circular sheets with the diameter of 19 mm;
(2) and (3) oxidation: immersing 5 pieces of polyolefin diaphragms prepared in the step (1) into concentrated nitric acid or a mixed solution consisting of hydrogen peroxide and potassium peroxodisulfate solution, continuously stirring, and carrying out oxidation treatment on the surfaces of the diaphragms to prepare densely distributed active sites on the surfaces of the diaphragms;
(3) mixing and mixing solvent: mixing ethanol and deionized water into a mixed solvent, wherein the volume usage ratio of the ethanol to the deionized water is 1: 1;
(4) preparing a transition metal salt solution: adding a transition metal salt into the mixed solvent prepared in the step (3), and continuously stirring to fully dissolve the salt;
(5) compounding: immersing the diaphragm treated in the step (2) into the transition metal salt solution prepared in the step (4), then dropwise adding hydrogen sulfuric acid, and continuously stirring to graft a transition metal sulfide onto an active site of the diaphragm;
(6) cleaning and drying: and (5) fishing out the diaphragm processed in the step (5), washing the diaphragm by deionized water for many times, then washing the diaphragm by absolute ethyl alcohol for many times, and then drying the diaphragm in vacuum to obtain the polyolefin diaphragm modified by the transition metal sulfide.
2. The method for preparing the high-performance polyolefin composite battery separator according to claim 1, characterized in that: in the step (2), 100mL of concentrated nitric acid with the concentration of 98% is required;
the hydrogen peroxide solution is a hydrogen peroxide aqueous solution with the hydrogen peroxide content of 30 percent by mass, the concentration of the potassium peroxodisulfate solution is 0.05mol/L, and the mixed solution is prepared by mixing 50mL of hydrogen peroxide and 50mL of potassium peroxodisulfate solution;
the stirring time is 3-3.5 h.
3. The method for preparing the high-performance polyolefin composite battery separator according to claim 2, characterized in that: the polyolefin diaphragm in the step (1) is a polyethylene diaphragm, a polypropylene diaphragm or a polyethylene and polypropylene composite diaphragm.
4. The method for preparing a high-performance polyolefin composite battery separator according to any one of claims 1 to 3, characterized in that: in the step (4), 0.5-1.2 g of transition metal salt is added into 100mL of mixed solvent, and stirring is carried out for 10 min; the transition metal salt is Ce (SO)4)2、FeSO4·7H2O、MnSO4·H2O、(CH3COO)2Cd·2H2O、NiCl2·6H2O or a combination of any two or more of O.
5. The method for preparing the high-performance polyolefin composite battery separator according to claim 4, wherein: the concentration of the hydrogen sulfuric acid used in the step (5) is 0.1mol/L, the volume is 20-30 mL, the stirring time is 2-2.5 h, and the temperature is room temperature.
6. The method for preparing the high-performance polyolefin composite battery separator according to claim 5, wherein: step (6) is vacuum drying at 45 ℃ for 24 h.
7. A lithium sulfur battery comprising a polyolefin separator, characterized in that: the polyolefin separator is prepared by the preparation method of the high-performance polyolefin composite battery separator as claimed in any one of claims 1 to 6.
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| CN112803116B (en) * | 2021-02-20 | 2023-04-21 | 天津谦同新能源科技有限公司 | Lithiation treatment method of diaphragm and diaphragm material treated by lithiation treatment method |
| CN116315463B (en) * | 2023-05-11 | 2023-08-18 | 中创新航科技集团股份有限公司 | Lithium battery |
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| CN1591934A (en) * | 2003-08-29 | 2005-03-09 | 三星Sdi株式会社 | Positive electrode with polymer film and lithium-sulfur cell using the positive electrode |
| CN104151588A (en) * | 2014-07-14 | 2014-11-19 | 浙江大学 | Diaphragm for lithium-sulfur batteries and preparation method of lithium-sulfur batteries |
| CN106848161A (en) * | 2017-01-05 | 2017-06-13 | 清华大学深圳研究生院 | Lithium-sulfur cell barrier film and the lithium-sulfur cell comprising the barrier film |
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| CN1591934A (en) * | 2003-08-29 | 2005-03-09 | 三星Sdi株式会社 | Positive electrode with polymer film and lithium-sulfur cell using the positive electrode |
| CN104151588A (en) * | 2014-07-14 | 2014-11-19 | 浙江大学 | Diaphragm for lithium-sulfur batteries and preparation method of lithium-sulfur batteries |
| CN106848161A (en) * | 2017-01-05 | 2017-06-13 | 清华大学深圳研究生院 | Lithium-sulfur cell barrier film and the lithium-sulfur cell comprising the barrier film |
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