CN111682147A - Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and shuttle effect and preparation method thereof - Google Patents
Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and shuttle effect and preparation method thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention belongs to the technical field of battery diaphragm materials, and particularly relates to a double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and shuttle effect and a preparation method thereof. The double-coating membrane comprises a membrane and coating materials coated on two sides of the membrane, wherein the coating materials comprise Zn-MOF materials and ZnNC carbon materials; the preparation method comprises the following steps: the preparation method comprises the steps of preparing a Zn-MOF powder material and a ZnNC carbon material, respectively preparing the Zn-MOF powder material and the ZnNC carbon material into slurry, and coating the slurry on two sides of a battery diaphragm to obtain a double-coating diaphragm, wherein the double-coating diaphragm simultaneously has the protection effect on a lithium cathode and the inhibition effect on lithium polysulfide shuttling, is applied to a lithium sulfur battery, and has excellent electrochemical cycling stability through electrochemical detection.
Description
Technical Field
The invention belongs to the technical field of battery diaphragm materials, and particularly relates to a double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and shuttle effect and a preparation method thereof.
Background
The lithium-sulfur battery is a secondary battery which takes elemental sulfur or a sulfur-containing material as a positive electrode and takes metallic lithium or a lithium storage material as a negative electrode. The lithium-sulfur battery charging and discharging process involves multistep complex electrochemical reaction, active substances undergo a solid-liquid-solid phase complex phase transformation process, and some troublesome problems are generated to seriously restrict the practical application of the lithium-sulfur battery, and mainly comprise: the problems of poor conductivity of the positive active material sulfur and the product lithium sulfide, volume expansion, rapid capacity attenuation caused by polysulfide ion shuttle effect, and poor safety caused by lithium dendrite and pulverization are solved by people in the aspects of the key materials of lithium batteries such as the positive electrode, the negative electrode, the diaphragm, electrolyte and the like aiming at the key problems, but the research and development of high-performance lithium sulfur batteries are still puzzled by the lithium dendrite and polysulfide ion shuttle effect.
The lithium-sulfur battery uses metal lithium as a negative electrode, and because the lithium ions with uneven surfaces are precipitated, dendritic crystals are easy to grow, pulverization and lithium death of the metal lithium are caused, and finally, the diaphragm is pierced, so that the battery is subjected to safety accidents such as short circuit, fire and the like.
Obviously, the successful solution of the safety problem of the lithium negative electrode is the premise and guarantee of the lithium-sulfur battery going to the practical application. In order to protect the lithium negative electrode, additives such as inorganic salts or organic small molecules are usually added into the electrolyte to form a stable SEI film on the surface of the electrolyte, and a functional coating capable of inducing the uniform deposition of lithium ions can also be formed on the lithium negative electrode or a separator facing the lithium negative electrode in situ/ex situ. The high task set coats the copper nitride precursor colloid solution on the surface of lithium, and lithium ions which are rapidly conducted and rich in Li can be generated through in-situ reaction along with the proceeding of the lithium extracting and embedding process3N, artificial interface. The artificial SEI film is used for lithium-copper battery at a current density of 1mA cm-2The cycle efficiency in the carbonate electrolyte system is improved to 97.4%, and the service life of the lithium titanate battery matched with the system is prolonged by nearly 40%. Guo Yuguo et al use polyphosphoric acid to treat lithium metal to form Li on surface thereof3PO4The base film, which acts as a physical barrier between the lithium metal and the electrolyte, prevents their contact reactions, reducing the corrosion consumption of metallic lithium. Li3PO4High ionic conductivity, low surface energy and uniform current distribution, effectively induces the uniform deposition of lithium ion flow and inhibits the formation of dendritic lithium. Living beings of Nanjing university such as Liujie utilize the biomembrane in the eggshell as the functional layer to coat on the diaphragm, because the biomembrane is to the attraction of positive and negative charge, when facing lithium negative pole, can make lithium ion deposit the distribution on its surface evenly, inhibit the growth of lithium dendrite betterly.
The lithium polysulphides produced in the reaction have to pass through the separator before they can be shuttled to the negative electrode, which means that separator modification is also an effective way of inhibiting shuttling of lithium polysulphides. Because the preparation process is simple, the structure is stable, the coating weight is light, and the influence of the coating of a functional coating on the common diaphragm on the overall energy density of the battery is small, the method is an effective method for inhibiting the shuttle of polysulfide ions.
Through the research of the above documents, it can be understood that the application of the functional coating on the common separator can not only effectively inhibit the dendrite problem of the lithium negative electrode in the lithium-sulfur battery, but also better eliminate the shuttle effect of lithium polysulfide. However, the reports in the literature or the invention only consider one of the problems, and the construction of the multifunctional diaphragm coating capable of solving the two bottleneck problems is still rarely reported.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a double-coated separator that simultaneously suppresses dendrite and shuttle effects of lithium, and that has a protective effect on a lithium negative electrode and a suppression effect on shuttle of lithium polysulfide, and a method for preparing the same.
The technical content of the invention is as follows:
the invention provides a double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and shuttle effect, which comprises a diaphragm and coating materials coated on two sides of the diaphragm, wherein the coating materials comprise Zn-MOF materials and ZnNC carbon materials;
the invention also provides a preparation method of the double-coating diaphragm for simultaneously inhibiting the dendritic crystal and shuttle effect of lithium, which comprises the following steps: preparing a Zn-MOF powder material and a ZnNC carbon material, respectively preparing the Zn-MOF powder material and the ZnNC carbon material into slurry, and coating the slurry on two sides of a battery diaphragm to obtain a double-coating diaphragm, which is also called a Janus diaphragm;
the preparation method of the Zn-MOF powder material comprises the following steps: dissolving adenine to obtain a solution A, dissolving 4, 4-biphenyldicarboxylic acid to obtain a solution B, dissolving zinc acetate and polyvinylpyrrolidone to obtain a solution C, mixing the solution A, the solution B and the solution C, adding a mixed organic solvent to carry out stirring reaction, centrifuging, washing and drying to obtain a Zn-MOF powder material;
the mixed organic solvent comprises a mixture of N, N-Dimethylformamide (DMF), anhydrous methanol and water;
the mixing ratio of the solution A to the solution B to the solution C is 1: (1-4);
the preparation method of the ZnNC carbon material comprises the following steps: calcining the Zn-MOF powder material in a high-temperature inert gas atmosphere to obtain a ZnNC carbon material;
the operation of respectively mixing the Zn-MOF powder material and the ZnNC carbon material into slurry comprises the steps of mixing the Zn-MOF powder material with a binder and N-methylpyrrolidone to prepare slurry 1, mixing the ZnNC carbon material with the binder and the N-methylpyrrolidone to prepare slurry 2, and respectively coating the slurry 2 on two sides of a diaphragm, wherein the obtained double-coating diaphragm is the Janus diaphragm, and the binder comprises a PVDF binder.
The invention has the following beneficial effects:
the double-coating diaphragm has the protection effect on the lithium cathode and the inhibition effect on the lithium polysulfide shuttling, the common diaphragm cannot realize the effective and uniform precipitation of lithium dendrites, the lithium dendrites are easy to rapidly puncture the diaphragm, and the battery is short-circuited;
the prepared double-coating diaphragm is applied to a lithium-sulfur battery, and has excellent electrochemical cycling stability through electrochemical detection.
Drawings
FIG. 1 is a scanning electron microscope image of Zn-MOF powder material;
FIG. 2 is a powder diffraction pattern of a Zn-MOF powder material;
FIG. 3 is a scanning electron micrograph of ZnNC carbon material;
FIG. 4 is a powder diffraction pattern of ZnNC carbon material;
FIG. 5 is a cross-sectional electron micrograph of a Janus membrane;
FIG. 6 shows the current density of 1mA/cm for a Zn-MOF coated separator modified lithium symmetric battery2Capacity of 2 mAh/cm2Long cycle performance plot of;
fig. 7 is a graph comparing the cycling performance of lithium sulfur batteries assembled with different separators at a current density of 2C.
Detailed Description
The present invention is described in further detail in the following description of specific embodiments and the accompanying drawings, it is to be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and modifications thereof by those skilled in the art after reading this disclosure that are equivalent to the above described embodiments.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
Example 1
Preparation of a double-coated separator that simultaneously suppresses lithium dendrite and shuttle effects:
1) preparing a Zn-MOF powder material: dissolving 1mmol of adenine and 1mmol of 4, 4-biphenyldicarboxylic acid (the two are in a molar ratio of 1:1) in 20mL of DMF respectively and ultrasonically dissolving to obtain a solution A and a solution B for later use, dissolving 1mmol of zinc acetate and 1g of polyvinylpyrrolidone in 20mL of DMF and ultrasonically dissolving to obtain a solution C for later use, mixing the solution A, the solution B and the solution C in a volume ratio of 1:1:1, adding activated and dispersed DMF, methanol and deionized water in a volume ratio of 5:4:1, and stirring at room temperature for 12 hours;
after the reaction is stopped, centrifuging for 5min at 8000r/min to obtain white powder, washing the white powder with DMF and MeOH in sequence, and drying the white powder in an oven to obtain the Zn-MOF powder material, wherein the Zn-MOF powder material is shown in a scanning electron microscope image of the Zn-MOF powder material in figure 1 and forms a uniform honeycomb sphere shape, and figure 2 is a powder diffraction image of the Zn-MOF powder material and shows that the Zn-MOF powder material is completely matched with the powder diffraction image;
2) preparing a ZnNC carbon material: calcining the Zn-MOF powder material prepared in the step 1) in a tube furnace in a nitrogen atmosphere, calcining at 800 ℃ for 2h, raising the temperature at a speed of 5 ℃/min, and obtaining a product ZnNC carbon material after the calcination, wherein the ZnNC carbon material is a scanning electron microscope image of the ZnNC carbon material as shown in figure 3 and forms a uniform honeycomb sphere shape, and figure 4 is a powder diffraction image of the ZnNC carbon material, so that the ZnNC carbon material is an amorphous carbon material and is completely matched with the amorphous carbon material;
3) preparing a double-coating diaphragm: dispersing the Zn-MOF powder material and the PVDF binder in the step 1) into slurry 1 by using an N-methylpyrrolidone solution according to the ratio of 6:1, and dispersing the ZnNC carbon material and the PVDF binder in the step 2) into slurry 2 by using an N-methylpyrrolidone solution according to the ratio of 6: 1;
taking a common commercial Celgard diaphragm, coating the diaphragm on one side of the diaphragm by using the slurry 1, drying the diaphragm for 24h in a vacuum drying box at 60 ℃, coating the diaphragm on the other side of the diaphragm by using the slurry 2, drying the diaphragm for 24h in the vacuum drying box at 60 ℃, and cutting the diaphragm into a wafer size with the diameter of 19mm by using a slicing machine to obtain the double-coating diaphragm-Janus diaphragm, wherein a sectional electron microscope picture of the Janus diaphragm is shown in figure 5, wherein the Zn-MOF coating is 7.27 mu m thick, the ZnNC coating is 6.55 mu m thick, and the Celgard with the thickness of 25 mu m is arranged in the middle.
Example 2
Preparation of a double-coated separator that simultaneously suppresses lithium dendrite and shuttle effects:
1) preparing a Zn-MOF powder material: dissolving 1mmol of adenine and 1mmol of 4, 4-biphenyldicarboxylic acid in 20mL of DMF respectively for ultrasonic dissolution for later use, dissolving 1mmol of zinc acetate and 1g of polyvinylpyrrolidone in 20mL of DMF for ultrasonic dissolution for later use, mixing the three DMF dissolved solutions according to the volume ratio of 1:1:2, adding activated and dispersed DMF, methanol and deionized water according to the volume ratio of 5:4:1, and stirring at room temperature for 18 hours;
after the reaction is stopped, centrifuging for 5min at 8000r/min to obtain white powder, washing the white powder with DMF and MeOH in sequence, and drying the white powder in an oven to obtain a Zn-MOF powder material;
2) preparing a ZnNC carbon material: calcining the Zn-MOF powder material prepared in the step 1) in a tubular furnace in a nitrogen atmosphere at 800 ℃ for 4h, wherein the heating rate is 5 ℃/min, and obtaining a product ZnNC carbon material after the calcination is finished;
3) preparing a double-coating diaphragm: dispersing the Zn-MOF powder material and the PVDF binder in the step 1) into slurry 1 by using an N-methylpyrrolidone solution according to the ratio of 6:1, and dispersing the ZnNC carbon material and the PVDF binder in the step 2) into slurry 2 by using an N-methylpyrrolidone solution according to the ratio of 6: 1;
coating a common commercial Celgard diaphragm on one side of the diaphragm by using the slurry 1, drying for 24h in a vacuum drying oven at the temperature of 60 ℃, coating the other side of the diaphragm by using the slurry 2, drying for 24h in the vacuum drying oven at the temperature of 60 ℃, and cutting into a wafer with the diameter of 19mm by using a slicing machine to obtain the double-coating diaphragm-Janus diaphragm.
Example 3
Preparation of a double-coated separator that simultaneously suppresses lithium dendrite and shuttle effects:
1) preparing a Zn-MOF powder material: dissolving 1mmol of adenine and 1mmol of 4, 4-biphenyldicarboxylic acid in 20mL of DMF respectively for standby ultrasonic dissolution, dissolving 1mmol of zinc acetate and 1g of polyvinylpyrrolidone in 20mL of DMF for standby ultrasonic dissolution, mixing the three DMF dissolved solutions according to the volume ratio of 1:1:4, adding activated and dispersed DMF, methanol and deionized water according to the volume ratio of 5:4:1, and stirring at room temperature for 24 hours;
after the reaction is stopped, centrifuging for 5min at 8000r/min to obtain white powder, washing the white powder with DMF and MeOH in sequence, and drying the white powder in an oven to obtain a Zn-MOF powder material;
2) preparing a ZnNC carbon material: calcining the Zn-MOF powder material prepared in the step 1) in a tubular furnace in a nitrogen atmosphere at 800 ℃ for 6 hours at the heating rate of 5 ℃/min to obtain a product ZnNC carbon material after the calcination is finished;
3) preparing a double-coating diaphragm: dispersing the Zn-MOF powder material and the PVDF binder in the step 1) into slurry 1 by using an N-methylpyrrolidone solution according to the ratio of 6:1, and dispersing the ZnNC carbon material and the PVDF binder in the step 2) into slurry 2 by using an N-methylpyrrolidone solution according to the ratio of 6: 1;
coating a common commercial Celgard diaphragm on one side of the diaphragm by using the slurry 1, drying for 24h in a vacuum drying oven at the temperature of 60 ℃, coating the other side of the diaphragm by using the slurry 2, drying for 24h in the vacuum drying oven at the temperature of 60 ℃, and cutting into a wafer with the diameter of 19mm by using a slicing machine to obtain the double-coating diaphragm-Janus diaphragm.
The coating diaphragm is applied to the electrochemical performance test of the battery:
1. the Zn-MOF coated separator was used for electrochemical performance testing of lithium symmetric cells:
in a glove box, lithium sheets are respectively used as a positive electrode and a negative electrode, Celgard or Celgard coated with the Zn-MOF material prepared in the embodiment 1 is used as a diaphragm, 1.0M LiTFSI DOL/DME (v: v, 1:1) is used as electrolyte to assemble a lithium-lithium symmetric battery, and the prepared lithium battery is applied to test data of an electrochemical test system;
as shown in FIG. 6, which is a symmetric lithium-lithium battery coated with a Zn-MOF separator, the current density is 1mA/cm2Long cycle performance plot of (1) mA/cm, showing that2，2 mAh/cm2The polarization was stabilized below 89mV, indicating that the Zn-MOF coating could better suppress lithium dendrites and thus protect the lithium negative electrode, compared to a commercial separator that was not coated with the Zn-MOF material prepared in example 1, which did not achieve efficient and uniform deposition of lithium dendrites, and the polarization voltage reached approximately 300mV when the cycle was less than 400 h. The Zn-MOF coating can effectively realize the uniform deposition of the lithium negative electrode, thereby inhibiting the growth of lithium dendrites.
2. The double-coating membrane-Janus membrane of the invention is used for the electrochemical performance test of a lithium-sulfur battery:
reacting S and Ketjen black in a reaction kettle at 155 ℃ for 24 hours according to the ratio of 1:4 to prepare a C/S compound, dispersing the C/S compound and a Super-P, LA132 binder in a normal propyl alcohol solution according to the ratio of 8:1:1 to prepare slurry, coating the slurry on an aluminum foil, and drying in a vacuum drying oven at 60 ℃ for 24 hours;
cutting into electrode discs with diameter of 12mm by a slicer, and preparing into electrode discs with sulfur loading of 5mg/cm by scrapers with different thicknesses2The pole piece of (2). In a glove box, the prepared pole piece is taken as a positive electrode, a lithium piece is taken as a negative electrode, Celgard or a Janus diaphragm coated with double coating materials is taken as a diaphragm, 1.0M LiTFSI DOL/DME (v: v, 1:1) is taken as electrolyte, and a CR-2302 button cell is assembled, wherein a Zn-MOF coating layer faces to the lithium negative electrode, a ZnNC coating layer faces to the sulfur positive electrode, and the prepared lithium sulfur cell is applied to electrochemical test system test data;
as shown in fig. 7, which is a graph comparing the cycle performance at a current density of 2C for lithium-sulfur cells assembled with differently coated separators, it can be seen that the performance of the Janus separator with a double coating is much better than that of the Celgard separator without a coating, or with only one of the Zn-MOF or ZnNC coatings. The Janus diaphragm assembled lithium-sulfur battery still has good cycling stability even under the current density of 2C, and can stably cycle to 1000 circles. The Janus membrane developed by the invention can effectively inhibit the lithium dendrite and shuttle effects at the same time.
Claims (8)
1. A double-coated separator for simultaneously suppressing lithium dendrite and shuttle effects, comprising a separator and coating materials coated on both sides of the separator, wherein the coating materials comprise a Zn-MOF material and a ZnNC carbon material.
2. A method for preparing a double-coated separator for simultaneously suppressing lithium dendrite and shuttling effects according to claim 1, comprising the steps of: preparing a Zn-MOF powder material and a ZnNC carbon material, respectively preparing the Zn-MOF powder material and the ZnNC carbon material into slurry, and coating the slurry on two sides of the battery diaphragm to obtain the double-coating diaphragm.
3. The preparation method of the double-coating membrane in claim 2, wherein the preparation of the Zn-MOF powder material comprises the following steps: dissolving adenine to obtain a solution A, dissolving 4, 4-biphenyldicarboxylic acid to obtain a solution B, dissolving zinc acetate and polyvinylpyrrolidone to obtain a solution C, mixing the solution A, the solution B and the solution C, adding a mixed organic solvent to carry out stirring reaction, centrifuging, washing and drying to obtain the Zn-MOF powder material.
4. The method for preparing a double coated membrane according to claim 3, wherein the mixed organic solvent comprises a mixture of N, N-Dimethylformamide (DMF), anhydrous methanol and water.
5. The method for preparing the double-coated separator according to claim 3, wherein the mixing ratio of the solution A, the solution B and the solution C is 1: (1-4).
6. The method for preparing the double-coated separator according to claim 2, wherein the preparation of the ZnNC carbon material comprises the steps of: and calcining the Zn-MOF powder material in a high-temperature inert gas atmosphere to obtain the ZnNC carbon material.
7. The preparation method of the double-coating membrane as claimed in claim 2, wherein the operation of respectively mixing the Zn-MOF powder material and the ZnNC carbon material into slurry comprises mixing the Zn-MOF powder material with a binder and N-methylpyrrolidone to prepare slurry 1, mixing the ZnNC carbon material with the binder and N-methylpyrrolidone to prepare slurry 2, and respectively coating the slurry 1 and the slurry 2 on two sides of the membrane to obtain the double-coating membrane.
8. The method of making a double coated membrane of claim 7 wherein the binder comprises a PVDF binder.
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| CN112635917A (en) * | 2020-12-29 | 2021-04-09 | 浙江大学 | High-strength functional diaphragm for alkali metal-based battery, preparation method of high-strength functional diaphragm and alkali metal-based battery |
| CN112670669A (en) * | 2020-12-23 | 2021-04-16 | 华南农业大学 | Nitrogen-doped carbon-coated Co and/or Co3Application of ZnC composite material in preparation of lithium-sulfur battery diaphragm |
| CN112670664A (en) * | 2020-12-21 | 2021-04-16 | 广东微电新能源有限公司 | Diaphragm, preparation method thereof and chemical battery |
| CN112750983A (en) * | 2020-12-31 | 2021-05-04 | 合肥国轩高科动力能源有限公司 | Three-dimensional composite lithium metal negative electrode, preparation method thereof and lithium battery |
| CN113582217A (en) * | 2021-06-08 | 2021-11-02 | 湖南师范大学 | Preparation method of ZnO/carbon composite interlayer |
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