CN111682147B - 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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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 multi-step complex electrochemical reactions, active materials undergo a solid-liquid-solid phase complex phase transformation process, and some troublesome problems generated seriously restrict the practical application of the lithium-sulfur battery, mainly comprising: aiming at the key problems of poor conductivity of a positive active substance sulfur and a product lithium sulfide, volume expansion, and poor safety caused by rapid capacity attenuation and lithium dendrite and pulverization caused by a multi-sulfur ion shuttle effect, people provide various solutions for key materials of lithium batteries such as a positive electrode, a negative electrode, a diaphragm, an electrolyte and the like, but the research and development of high-performance lithium sulfur batteries are still puzzled by the lithium dendrite and multi-sulfur 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 lithium ion flow to be uniformly deposited can also be formed on the lithium negative electrode or a separator facing the lithium negative electrode in situ/ex situ. For example, cui Yi topic group coats the copper nitride precursor colloid solution on the lithium surface, and can generate lithium ions which are rapidly conducted and rich in Li through in-situ reaction along with the proceeding of the lithium extraction process 3 N, artificial interface. The artificial SEI film enables a lithium-copper battery to be manufactured at a current density of 1mA cm -2 The 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 and the like, lithium metal is treated with polyphosphoric acid to form Li on the surface thereof 3 PO 4 The base film, which acts as a physical barrier between the lithium metal and the electrolyte, prevents their contact reactions, reducing the corrosive consumption of metallic lithium. Li 3 PO 4 High 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. The membrane is coated with a biomembrane in an eggshell as a functional layer in the university of Nanjing Liu Jie, and because the biomembrane attracts positive and negative charges, when facing a lithium cathode, lithium ions can be uniformly deposited and distributed on the surface of the membrane, and the growth of lithium dendrites is well inhibited.
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 suppressing 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, the solution B and the solution C is 1:1: (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 battery 2 Capacity of 2 mAh/cm 2 Long cycle performance ofA drawing;
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 standby, dissolving 1mmol of zinc acetate and 1g of polyvinylpyrrolidone in 20mL of DMF and ultrasonically dissolving to obtain a solution C for standby, mixing the solution A, the solution B and the solution C in a volume ratio of 1;
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 proportion 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 proportion 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 standby, dissolving 1mmol of zinc acetate and 1g of polyvinylpyrrolidone in 20mL of DMF for ultrasonic dissolution for standby, mixing the three DMF solutions in a volume ratio of 1;
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 proportion 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 proportion 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-coating membrane for simultaneously inhibiting lithium dendrite and shuttle effects:
1) Preparing a Zn-MOF powder material: dissolving 1mmol of adenine and 1mmol of 4, 4-biphenyldicarboxylic acid in DMF (20 mL) respectively for standby application by ultrasonic dissolution, dissolving 1mmol of zinc acetate and 1g of polyvinylpyrrolidone in 20mL of DMF for standby application by ultrasonic dissolution, mixing the three DMF solutions in a volume ratio of 1;
after the reaction is stopped, centrifuging for 5min at 8000r/min to obtain white powder, washing the white powder by 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 proportion 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 proportion 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 Zn-MOF materials prepared in example 1 is used as a diaphragm, 1.0M LiTFSI DOL/DME (v: v, 1:1) is used as electrolyte to assemble a lithium symmetric battery, and the prepared lithium battery is applied to electrochemical test system test data;
as shown in FIG. 6, it is a Zn-MOF coated lithium symmetric cell at a current density of 1mA/cm 2 Shows that it can be in the range of 1mA/cm 2 ，2 mAh/cm 2 The 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 is used for the electrochemical performance test of the lithium-sulfur battery:
reacting S and Ketjen black in a reaction kettle at 155 ℃ for 24 hours according to the proportion of 1:4 to prepare a C/S composite, dispersing the C/S composite and a Super-P, LA binder by using an n-propanol solution according to the proportion of 8;
cutting into electrode wafers with the diameter of 12mm by using a slicer, and respectively preparing the electrode wafers with the sulfur loading of 5mg/cm by using scrapers with different thicknesses 2 The 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 the CR-2302 button cell is assembled, wherein the Zn-MOF coating layer faces to the lithium negative electrode, and the ZnNC coating layer faces to the ZnNC coating layerThe sulfur anode applies the prepared lithium-sulfur battery to the test data of an electrochemical test system;
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 (3)
1. A preparation method of a double-coating diaphragm for simultaneously inhibiting lithium dendrite and shuttle effect is characterized by comprising 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;
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 mixing volume ratio of the solution A, the solution B and the solution C is 1:1 (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 1 and the slurry 2 on two sides of a diaphragm to obtain the double-coating diaphragm.
2. The method for preparing the double-coated separator according to claim 1, wherein the mixed organic solvent comprises a mixture of N, N-dimethylformamide, anhydrous methanol and water.
3. The method of making a double coated membrane of claim 1 wherein the binder comprises a PVDF binder.
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| CN112670664B (en) * | 2020-12-21 | 2023-11-03 | 广东微电新能源有限公司 | Separator, preparation method thereof and chemical battery |
| CN112670669B (en) * | 2020-12-23 | 2023-05-05 | 华南农业大学 | Nitrogen doped carbon coated Co and/or Co 3 Application of ZnC composite material in preparation of lithium-sulfur battery diaphragm |
| 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 |
| 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 |
| KR20220108505A (en) * | 2021-01-27 | 2022-08-03 | 주식회사 엘지에너지솔루션 | Separator for lithium secondary battery and method for preparing the same |
| 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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