CN111430789B - Method for reducing porosity of solid electrolyte layer and application thereof - Google Patents
Method for reducing porosity of solid electrolyte layer and application thereof Download PDFInfo
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- CN111430789B CN111430789B CN201911202976.6A CN201911202976A CN111430789B CN 111430789 B CN111430789 B CN 111430789B CN 201911202976 A CN201911202976 A CN 201911202976A CN 111430789 B CN111430789 B CN 111430789B
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
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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
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Abstract
The invention provides a method for reducing the porosity of a solid electrolyte layer and application thereof, wherein the method comprises the following steps: and carrying out isostatic compaction treatment on the solid electrolyte layer after film forming and drying. The method has the advantages of simple and convenient process, easy implementation and higher controllability, can apply higher pressure to the solid electrolyte layer on the premise of ensuring that the solid electrolyte layer is not damaged, deformed or folded, further can remarkably reduce the porosity of the solid electrolyte layer, and is more beneficial to the subsequent battery assembly process due to the flatness and no folds of the electrolyte layer compacted by the method.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a method for reducing the porosity of a solid-state electrolyte layer and application thereof.
Background
The solid-state battery adopts non-flammable solid electrolyte to replace flammable organic liquid electrolyte, so that the safety of a battery system is greatly improved, the high-energy positive and negative electrodes can be better adapted, the weight of the system is reduced, and the synchronous improvement of the energy density is realized. Among various new battery systems, solid-state batteries are the next-generation technology closest to the industrialization, which has become a consensus of the industry and the scientific community.
The porosity of the electrolyte layer of the all-solid-state battery is reduced, so that the conductivity of the electrolyte layer can be improved, the impedance is reduced, the overall size of the battery is favorably reduced, and the volume energy density of the solid-state battery is improved. However, at present, a double-roller counter-pressing device is generally adopted to reduce the porosity of the electrolyte layer of the all-solid-state battery, but the pressure applied by the rolling device is low, so that the porosity of the electrolyte layer cannot be reduced remarkably; the electrolyte layer is easy to wrinkle in the rolling process, and the double-roller counter-pressing equipment is also easy to cause the stretching of the electrolyte, so that the electrolyte is damaged; in addition, after the electrolyte layer is rolled by using a rolling device, the electrolyte layer is easily curled, which makes the subsequent battery assembly process difficult.
Disclosure of Invention
In view of the above, the present invention is directed to a method for reducing the porosity of a solid electrolyte layer, so as to significantly reduce the porosity of the solid electrolyte layer and reduce the damage probability of the electrolyte layer during compaction. In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the invention provides a method for reducing the porosity of a solid electrolyte layer. According to an embodiment of the invention, the method comprises: and carrying out isostatic compaction treatment on the solid electrolyte layer after film formation and drying.
Further, the method for reducing the porosity of the solid electrolyte layer further comprises: and carrying out first rolling treatment on the film-formed and dried solid electrolyte layer by using a rolling device in advance before carrying out isostatic pressing compaction treatment.
Further, the method for reducing the porosity of the solid electrolyte layer further comprises: and performing second rolling treatment on the isostatic-pressing compacted solid electrolyte layer by using a rolling device.
Further, the first roll pressing treatment reduces the porosity of the solid electrolyte layer by not more than 25% of the porosity of the solid electrolyte layer reduced by the isostatic compaction treatment.
Further, the second roll compaction reduces the porosity of the solid electrolyte layer by no more than 25% of the porosity of the solid electrolyte layer reduced by the isostatic compaction.
Further, the isostatic compaction process comprises: (1) placing the solid electrolyte layer subjected to film forming and drying/the solid electrolyte layer subjected to first rolling treatment in a sealed elastic die; (2) and carrying out isostatic compaction treatment on the sealed elastic die by using a liquid medium or a gaseous medium.
Further, the liquid medium is hydraulic oil or water.
Further, the isostatic compaction treatment is a cold isostatic compaction treatment or a hot isostatic compaction treatment.
Further, the pressure of the isostatic compaction treatment is 3-700 MPa, the temperature is 20-150 ℃, and the time is 0.5-180 min.
Further, the equipment adopted by the isostatic pressing treatment is cold isostatic pressing equipment or isostatic pressing equipment with heating and temperature control functions.
Further, the cold isostatic pressing equipment is cold isostatic pressing equipment adopting a wet bag method or cold isostatic pressing equipment adopting a dry bag method.
Further, the solid electrolyte layer is a self-supporting structure or a composite supporting structure by means of a support.
Further, the solid electrolyte layer includes a solid electrolyte material, a binder, and an ion conductor.
Further, the solid electrolyte layer includes a solid electrolyte material, a binder, an ionic conductor, a polymeric support, and/or a non-polymeric support.
Further, the solid electrolyte material is at least one selected from a sulfide electrolyte, a halogen electrolyte, and an oxide electrolyte.
Compared with the prior art, the method for reducing the porosity of the solid electrolyte layer has at least the following advantages: (1) on the premise of ensuring that the solid electrolyte layer is not damaged, deformed or folded, the pressure applied to the solid electrolyte layer can be higher, and the porosity of the solid electrolyte layer can be obviously reduced, so that on one hand, the conductivity of the electrolyte layer can be obviously improved, the impedance can be reduced, the internal resistance of the battery can be effectively reduced, and the electrochemical performance of the battery can be improved; on the other hand, the overall size of the battery is reduced, so that the volume energy density of the solid-state battery is remarkably improved; (2) the original shape of the solid electrolyte can be kept, the damage probability of the electrolyte layer in the compaction process is obviously reduced, and the electrolyte layer compacted by the method is flat and free of wrinkles, so that the method is more beneficial to the subsequent battery assembly process; (3) the method has the advantages of higher controllability, simple and convenient process, easy implementation and suitability for industrial production.
Another object of the present invention is to provide a solid electrolyte layer to improve the electrochemical performance and volumetric energy density of the battery. In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the invention provides a solid electrolyte layer. According to an embodiment of the present invention, the solid electrolyte layer is obtained by the above method of reducing the porosity of the solid electrolyte layer.
Further, the porosity of the solid electrolyte layer is 2-50%, preferably 2-25%.
Further, the conductivity of the solid electrolyte layer was 10 -6 ～10 -2 S/cm。
Compared with the prior art, the solid electrolyte layer provided by the invention has at least the following advantages: the solid electrolyte layer has low porosity, can achieve high conductivity, is flat, free of wrinkles and free of deformation, and therefore when the solid electrolyte layer is used for preparing a battery, not only can the electrochemical performance of the battery be improved, but also the volume energy density of the solid battery can be remarkably improved, and the solid electrolyte layer is beneficial to the implementation of a battery assembly process.
Another object of the present invention is to provide a battery, which can reduce the difficulty of assembling the battery and improve the electrochemical performance and volumetric energy density of the battery. In order to achieve the purpose, the technical scheme of the invention is realized as follows: the invention provides a battery. According to an embodiment of the present invention, the battery has the above-described solid electrolyte layer or a solid electrolyte layer obtained by the above-described method of reducing the porosity of the solid electrolyte layer. Compared with the prior art, the battery provided by the invention has the advantages that the electrochemical performance is good, the volume energy density is high, and the assembly difficulty of the solid electrolyte layer and the pole piece is relatively low.
Another object of the present invention is to provide a vehicle to further improve the competitiveness of the vehicle. In order to achieve the purpose, the technical scheme of the invention is realized as follows: the invention provides a vehicle which is provided with the battery according to the embodiment of the invention. Compared with the prior art, the vehicle provided by the invention has stronger cruising ability.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a scanning electron microscope photograph of a compacted solid electrolyte layer in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of an uncompacted solid electrolyte layer in example 1 of the invention;
FIG. 3 is a graph comparing the porosity of a compacted solid electrolyte layer of example 1 and comparative example 1 of the present invention and an uncompacted solid electrolyte layer of example 1;
FIG. 4 is a graph comparing the resistance of a compacted solid electrolyte layer of example 1 and comparative example 1 of the present invention and an uncompacted solid electrolyte layer of example 1;
FIG. 5 is a scanning electron microscope photograph of a compacted solid electrolyte layer in example 2 of the present invention;
FIG. 6 is a scanning electron microscope image of an uncompacted solid electrolyte layer in example 2 of the present invention;
FIG. 7 is a graph comparing the porosity of compacted solid electrolyte layers of example 2 and comparative example 2 of the present invention and uncompacted solid electrolyte layers of example 2;
FIG. 8 is a graph comparing the resistance of a compacted solid electrolyte layer of example 2 of the present invention and comparative example 2 and an uncompacted solid electrolyte layer of example 2;
FIG. 9 is an impedance diagram of a solid electrolyte layer according to examples 3 to 4 of the present invention;
FIG. 10 is a graph showing a comparison of the impedances of the solid electrolyte layers of example 2 of the present invention and comparative examples 2 to 6.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
According to a first aspect of the invention, a method of reducing the porosity of a solid electrolyte layer is proposed. According to an embodiment of the invention, the method comprises: the solid electrolyte layer after film formation and drying is subjected to isostatic compaction, for example, by using an isostatic pressing device. Compared with the traditional method for processing the solid electrolyte layer by adopting a rolling method, the method for carrying out isostatic compaction processing on the solid electrolyte layer has higher controllability, and can enable solid electrolyte powder to be in closer contact, thereby obviously reducing the porosity of the solid electrolyte layer, improving the conductivity of the electrolyte layer and reducing the impedance, effectively reducing the internal resistance of the battery, improving the electrochemical performance of the battery, being beneficial to reducing the overall size of the battery and improving the volume energy density of the solid battery; in addition, the method can also keep the original shape of the solid electrolyte and prevent the electrolyte layer from being damaged, folded and deformed in the compaction process, thereby being more beneficial to the subsequent battery assembly process.
The above-described method for reducing the porosity of the solid electrolyte layer is described in detail below.
According to an embodiment of the present invention, the solid electrolyte layer after film formation and drying may be subjected to a first rolling process by a rolling device, and then the solid electrolyte layer after the first rolling process may be subjected to an isostatic pressing process by an isostatic pressing device. The inventor finds that, because the pressure applied by the rolling treatment is uneven mechanical force, if a rolling device is adopted to greatly reduce the porosity of the solid electrolyte layer at one time, the electrolyte layer is easy to wrinkle or damage, and the solid electrolyte layer is rolled for a plurality of times, the porosity of the solid electrolyte layer is gradually reduced by controlling the force of each rolling, the distance between rollers and the like, when the density of the solid electrolyte layer reaches a certain degree, the electrolyte layer is easy to wrinkle or damage, namely, the electrolyte layer is easy to damage, wrinkle and deform when the porosity of the solid electrolyte layer reaches the expected range by simply performing the rolling treatment on the solid electrolyte layer. The solid electrolyte layer after film forming and drying is subjected to slight rolling in advance before isostatic compaction treatment, so that when the porosity reduction of the solid electrolyte layer is low, the solid electrolyte layer cannot be damaged and deformed, the solid electrolyte layer after slight rolling is further subjected to isostatic compaction treatment on the basis, and the phenomena of damage, folding and deformation caused by uneven stress after the density of the solid electrolyte layer reaches a certain degree can be effectively avoided.
According to still another embodiment of the present invention, the porosity of the solid electrolyte layer may be reduced by the first rolling process by not more than 25%, preferably not more than 20% or 15%, of the porosity of the solid electrolyte layer by the isostatic pressing process, and the inventors found that if the strength of the first rolling process is too high, the solid electrolyte layer may be damaged, wrinkled or deformed.
According to yet another embodiment of the present invention, the method of reducing the porosity of the solid electrolyte layer may further include: and performing second rolling treatment on the isostatic-pressing compacted solid electrolyte layer by using a rolling device. The inventors have found that the solid electrolyte layer after the isostatic compaction treatment is uniformly compressed over the entire surface and in all directions, and no shear force is present in the interior thereof, and therefore, the porosity of the solid electrolyte layer can be further reduced while maintaining the original shape of the solid electrolyte layer by performing the light rolling treatment again on the solid electrolyte layer after the isostatic compaction treatment.
According to still another embodiment of the present invention, the porosity reduction amount of the solid electrolyte layer by the second rolling process may be not more than 25%, preferably not more than 15% or 10% of the porosity reduction amount of the solid electrolyte layer by the isostatic compaction process, and the inventors found that, since the density of the solid electrolyte layer after the isostatic compaction process is relatively high, if the strength of the second rolling process is too high, the solid electrolyte layer is also easily damaged, wrinkled or deformed, and in the present invention, by controlling the porosity reduction amount of the solid electrolyte layer after the second rolling process to be within the above range, the solid electrolyte layer can be further prevented from being damaged, wrinkled or deformed during the rolling process.
According to another embodiment of the present invention, the method for reducing the porosity of the solid electrolyte layer according to the present invention may include the following schemes: (1) carrying out isostatic pressing treatment on the solid electrolyte layer after film forming and drying by using isostatic pressing equipment; (2) carrying out first rolling treatment on the film-formed and dried solid electrolyte layer by using rolling equipment in advance, and carrying out isostatic pressing treatment on the solid electrolyte layer subjected to the first rolling treatment by using isostatic pressing equipment; (3) carrying out isostatic pressing treatment on the solid electrolyte layer after film forming and drying by using isostatic pressing equipment in advance, and carrying out second rolling treatment on the solid electrolyte layer after the isostatic pressing treatment by using rolling equipment; (4) and finally, carrying out second rolling treatment on the solid electrolyte layer subjected to isostatic pressing treatment by using a rolling device.
According to another embodiment of the present invention, the type of the rolling device in the present invention is not particularly limited, and those skilled in the art can select the rolling device according to actual needs, for example, the rolling device may be a double-roller counter-rolling device or the like.
According to yet another specific embodiment of the present invention, the isostatic compaction process may comprise: (1) placing the solid electrolyte layer subjected to film forming and drying/the solid electrolyte layer subjected to first rolling treatment in a sealed elastic die; (2) the sealing elastic die is subjected to isostatic compaction by using a liquid medium or a gaseous medium, and specifically, the sealing elastic die can be placed in the liquid medium or the gaseous medium, and the liquid medium or the gaseous medium applies pressure and temperature to the solid electrolyte layer, so that the compaction of the solid electrolyte layer is realized. Therefore, the stress uniformity of the solid electrolyte layer can be further improved, the surface of the solid electrolyte after isostatic compaction is smooth and free of wrinkles, and the stress concentration phenomenon does not exist in the solid electrolyte. In addition, the types of the liquid medium and the gaseous medium in the present invention are not particularly limited, and those skilled in the art can select them according to actual needs, for example, the liquid medium may be hydraulic oil or water.
According to yet another embodiment of the present invention, the method of reducing the porosity of the solid electrolyte layer may further include: carrying out first rolling treatment on the film-formed and dried solid electrolyte layer by using rolling equipment; placing the solid electrolyte layer subjected to the first rolling treatment in a sealed elastic die; carrying out isostatic compaction treatment on the sealed elastic die by using a liquid medium or a gaseous medium so as to obtain a solid electrolyte layer after the isostatic compaction treatment; and performing second rolling treatment on the isostatic-pressing compacted solid electrolyte layer by using a rolling device. The porosity of the solid electrolyte layer can thereby be further reduced.
According to still another embodiment of the present invention, the isostatic compaction treatment may have a pressure of 3 to 700MPa, a temperature of 20 to 150 ℃, and a time of 0.5 to 180min, for example, a pressure of 10MPa, 50MPa, 100MPa, 150MPa, 200MPa, 250MPa, 300MPa, 350MPa, 400MPa, 450MPa, 500MPa, 550MPa, 600MPa, or 650MPa, and a temperature of 30 ℃, 50 ℃, 70 ℃, 90 ℃, 110 ℃, 130 ℃, or 150 ℃, and the like, and the inventors found that the porosity of the solid electrolyte layer cannot be significantly reduced, and if the isostatic compaction treatment has an excessive pressure, not only the alternating network in the solid electrolyte layer is broken, and the solid electrolyte layer is deformed or damaged, but also the crystal structure in the solid electrolyte layer is collapsed, and the solid electrolyte layer is made conductive; if the temperature of the isostatic compaction treatment is too low, the binder in the solid electrolyte layer is difficult to soften, and compaction of the solid electrolyte layer is difficult to realize, and if the temperature of the isostatic compaction treatment is too high, the binder can flow in the solid electrolyte layer, so that the solid electrolyte layer is deformed; if the isostatic compaction process is carried out for too long, the efficiency of the whole process is reduced. In the invention, by controlling the pressure, the temperature and the time of the isostatic compaction treatment within the ranges, the porosity of the solid electrolyte layer can be obviously reduced on the premise of ensuring the conductivity and the flatness of the solid electrolyte layer, and the efficiency and the effect of the isostatic compaction treatment are improved.
According to another embodiment of the present invention, the isostatic pressing process may be a cold isostatic pressing process or a hot isostatic pressing process, and the equipment used in the isostatic pressing process may be a cold isostatic pressing equipment or an isostatic pressing equipment with heating and temperature control functions, so that the solid electrolyte layer may be subjected to the isostatic pressing process at normal temperature or under heating conditions. Preferably, the hot isostatic pressing treatment can be performed by using an isostatic pressing device with heating and temperature control functions, so that the temperature of the isostatic pressing treatment can be controlled to be close to the softening point of the binder in the solid electrolyte layer, and the efficiency and the effect of the pressing treatment can be further improved. Further, the cold isostatic pressing device may be a wet bag cold isostatic pressing device or a dry bag cold isostatic pressing device, so that the liquid medium or the gaseous medium may be used to apply pressure and temperature to the solid electrolyte layer, thereby implementing the isostatic pressing treatment of the solid electrolyte layer.
According to still another embodiment of the present invention, the structure of the solid electrolyte layer in the present invention is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the solid electrolyte layer may be a self-supporting structure or a composite support structure with a support, i.e., the membrane-forming manner may be self-supporting or supported with a support, wherein the solid electrolyte layer of the self-supporting structure may include a solid electrolyte material, a binder and an ion conductor, and the composite support structure with a support may include a solid electrolyte material, a binder, an ion conductor, a polymer support and/or a non-polymer support. Wherein the solid electrolyte layer may have lithium conductivity. In addition, the kind of the solid electrolyte material and the binder is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the solid electrolyte material may be at least one selected from a sulfide electrolyte, a halogen electrolyte, an oxide electrolyte, or other solid material having lithium electrical conductivity, the binder may be an aqueous binder or an oily binder, and further, for example, the binder may be polyvinylidene fluoride.
According to an embodiment of the present invention, the porosity of the solid electrolyte layer can be reduced to 2% by the above method for reducing the porosity of the solid electrolyte layer, and the conductivity of the solid electrolyte layer can reach 10 -6 ～10 -2 S/cm. When the solid electrolyte layer is used for preparing a battery, the electrochemical performance of the battery and the volume energy density of the solid battery can be obviously improved.
In summary, compared with the prior art, the method for reducing the porosity of the solid electrolyte layer of the present invention has at least the following advantages: (1) on the premise of ensuring that the solid electrolyte layer is not damaged, deformed or folded, the pressure applied to the solid electrolyte layer can be higher, and the porosity of the solid electrolyte layer can be obviously reduced, so that on one hand, the conductivity of the electrolyte layer can be obviously improved, the impedance can be reduced, the internal resistance of the battery can be effectively reduced, and the electrochemical performance of the battery can be improved; on the other hand, the overall size of the battery is reduced, so that the volume energy density of the solid-state battery is remarkably improved; (2) the original shape of the solid electrolyte can be kept, the damage probability of the electrolyte layer in the compaction process is obviously reduced, and the electrolyte layer compacted by the method is flat and free of wrinkles, so that the subsequent battery assembly process is facilitated; (3) the method has the advantages of higher controllability, simple and convenient process, easy implementation and suitability for industrial production.
According to a second aspect of the invention, a solid electrolyte layer is proposed. According to an embodiment of the present invention, the solid electrolyte layer is obtained by the above method of reducing the porosity of the solid electrolyte layer. Compared with the prior art, the solid electrolyte layer has at least the following advantages: the solid electrolyte layer has low porosity, can achieve high conductivity, and is flat and free of wrinkles and deformation, so that when the solid electrolyte layer is used for preparing a battery, the electrochemical performance of the battery can be improved, the volume energy density of the solid battery is remarkably improved, and the battery assembly process is facilitated.
According to an embodiment of the present invention, the porosity of the solid electrolyte layer may be 2 to 50%, preferably 2 to 25%, and the conductivity of the solid electrolyte layer may be 10 -6 ～10 -2 S/cm. The electrochemical performance of the battery and the volumetric energy density of the solid-state battery can thereby be further improved.
It should be noted that the features and effects described for the above method for reducing the porosity of the solid electrolyte layer are also applicable to the solid electrolyte layer, and are not described in detail herein.
According to a third aspect of the present invention, a battery is provided. According to an embodiment of the present invention, the battery has the above solid electrolyte layer or the solid electrolyte layer obtained by the above method for reducing the porosity of the solid electrolyte layer, wherein the battery may be an all-solid lithium battery or the like. Compared with the prior art, the battery has at least the following advantages: not only the electrochemical performance is good and the volume energy density is high, but also the assembly difficulty of the solid electrolyte layer and the pole piece is relatively low. It should be noted that the features and effects described for the solid electrolyte layer and the method for reducing the porosity of the solid electrolyte layer are also applicable to the battery, and are not described in detail herein.
According to a fourth aspect of the invention, a vehicle is proposed, which has the above-described battery according to an embodiment of the invention. Compared with the prior art, the vehicle has stronger cruising ability. It should be noted that the features and effects described for the above battery are also applicable to the vehicle, and are not described in detail herein.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(I) film formation and baking of solid electrolyte layer
Solid electrolyte material: a sulfide solid electrolyte;
adhesive: polyvinylidene fluoride
Solvent: n-methyl pyrrolidone
Film formation method: self-supporting
Dissolving sulfide solid electrolyte and a binder in a solvent according to a certain proportion, stirring into uniform slurry, coating the slurry, and drying in vacuum at 140 ℃ for 20h to obtain the solid electrolyte layer. The thickness of the electrolyte layer after film formation and drying was 185 μm.
(II) reducing the porosity of the solid electrolyte layer
Firstly, carrying out first rolling compaction on the formed and dried electrolyte layer by a double-roller counter-pressure device: the spacing between the rolls was adjusted to 170 μm, the temperature between the rolls was 90 ℃ and the number of rolling times was 3. And then carrying out cold isostatic pressing treatment on the electrolyte layer subjected to the first rolling compaction: and (3) putting the solid electrolyte layer in the composite film, vacuumizing the composite film, putting the composite film in a wet bag method cold isostatic pressing device, respectively compacting the composite film at a certain pressure for 15 minutes, and taking out the electrode solid electrolyte layer, wherein the hydraulic pressure is 160MPa, the hydraulic time is 15 minutes, and the temperature is 20 ℃.
Comparative example 1
The difference from example 1 is that:
(II) reducing the porosity of the solid electrolyte layer
Performing first rolling compaction on the electrolyte layer after film formation and drying by using a double-roller counter-pressing device: the spacing between the two rollers is adjusted to be 170 micrometers, the temperature of the two rollers is 90 ℃, the rolling times are 3 times, the rolling pressure is 10MPa, and the solid electrolyte layer of the electrode is taken out.
And (3) performance testing:
1.1, the sulfide solid electrolyte layer of example 1 was subjected to scanning electron microscope tests without compaction treatment (0MPa) and without compaction treatment, and the test results are shown in fig. 1 and 2.
As can be seen from fig. 2, the solid electrolyte on the solid electrolyte layer that has not been subjected to the compaction treatment is loosely packed. As can be seen from fig. 1, after the compaction treatment, the morphology of the solid electrolyte becomes dense and the porosity of the solid electrolyte layer is significantly reduced.
1.2, the porosity of the solid electrolyte layer obtained in test example 1 without the compaction treatment (0MPa) and the compaction treatment (160MPa) and the porosity of the solid electrolyte layer obtained in comparative example 1 with the compaction treatment (10MPa) were measured by a mercury porosimeter, and the results are shown in fig. 3.
As can be seen from fig. 3, the porosity of the solid electrolyte layer without compaction in example 1 is large, about 45.5%; the porosity of the solid electrolyte layer after the roll compaction treatment at a pressure of 10MPa in comparative example 1 was about 31.6%; the porosity of the solid electrolyte layer after the roll compaction and isostatic compaction treatment in example 1 can reach about 19.8%, and the porosity is significantly reduced. It is thus demonstrated that the combined isostatic and rolling of the inventive examples can achieve porosities far exceeding those obtained by the prior art compaction processes at conventional pressures.
1.3, the solid electrolyte layer of example 1 without compaction treatment (0MPa) and without compaction treatment (160MPa) and the solid electrolyte layer of comparative example 1 after compaction treatment (10MPa) were subjected to impedance performance test by using an ac impedance meter, and the test results are shown in fig. 4.
As can be seen from fig. 4, the adoption of the combination of isostatic pressing and rolling in the embodiment of the invention can significantly reduce the impedance of the electrolyte layer, so that the resistance of the battery in the charging and discharging process is smaller, and the improvement of the conductivity and electrochemical performance of the material is facilitated.
Example 2
(I) film formation and baking of solid electrolyte layer
Solid electrolyte material: sulfide solid electrolyte
Adhesive: polyvinylidene fluoride
Solvent: n-methyl pyrrolidone
Film formation method: electrolyte layer with support
A support body: polypropylene film with net structure
Dissolving sulfide solid electrolyte and a binder in a solvent according to a certain proportion, stirring into uniform slurry, coating the slurry on a support, and drying in vacuum at 120 ℃ for 16h to obtain the solid electrolyte layer. The thickness of the electrolyte layer after film forming and drying is 135 microns, and the porosity is 47%.
(II) reducing the porosity of the solid electrolyte layer
And (4) carrying out cold isostatic pressing treatment on the dried electrolyte layer. And the hydraulic pressure is 350MPa, the hydraulic time is 20 minutes, the temperature is 20 ℃, specifically, the solid electrolyte layer is placed in the composite film, the composite film is vacuumized, then the composite film is placed in a cold isostatic pressing device of a wet bag method, the solid electrolyte layer is compacted under the pressure of 350MPa, the hydraulic time is 20 minutes, and the electrode solid electrolyte layer is taken out.
Comparative example 2
The difference from example 2 is that:
(II) reducing the porosity of the solid electrolyte layer
Performing first rolling compaction on the formed and dried electrolyte layer by using a double-roller counter-pressing device: the spacing between the two rollers is adjusted to be 170 micrometers, the temperature of the two rollers is 90 ℃, the rolling times are 3 times, the rolling pressure is 10MPa, and the solid electrolyte layer of the electrode is taken out.
And (3) performance testing:
2.1 scanning electron microscopy was used to test the sulfide solid electrolyte layer of example 2 without (0MPa) and without compaction, the results of which are shown in fig. 5 and 6.
As can be seen from fig. 6, the solid electrolyte on the solid electrolyte layer without being subjected to the compaction treatment is loosely packed. As can be seen from fig. 5, after the compaction treatment, the morphology of the solid electrolyte becomes dense and the porosity of the solid electrolyte layer is significantly reduced.
2.2, the porosity of the solid electrolyte layer obtained in test example 2 without compaction treatment (0MPa) and without compaction treatment (350MPa) and the porosity of the solid electrolyte layer obtained in comparative example 2 after compaction treatment (10MPa) are measured by a mercury porosimeter, and the results are shown in fig. 7.
As can be seen from fig. 7, the porosity of the solid electrolyte layer without compaction in example 2 was large, about 47%; in comparative example 2, the porosity of the solid electrolyte layer after the roll compaction treatment at a pressure of 10MPa was about 32.5%; the porosity of the solid electrolyte layer after the roll compaction and isostatic compaction treatment in example 2 can reach about 15.2%, and the porosity is significantly reduced. It is thus demonstrated that the combined isostatic and rolling of the inventive examples can achieve porosities far exceeding those obtained by the prior art compaction processes at conventional pressures.
2.3, the solid electrolyte layer of example 2 without compaction treatment (0MPa) and without compaction treatment and the solid electrolyte layer of comparative example 2 after compaction treatment were subjected to impedance performance test by using an ac impedance meter, and the test results are shown in fig. 8.
As can be seen from fig. 8, the adoption of the combination of isostatic pressing and rolling in the embodiment of the invention can significantly reduce the impedance of the electrolyte layer, so that the resistance of the battery in the charging and discharging process is smaller, and the improvement of the conductivity and electrochemical performance of the material is facilitated.
Example 3
The difference from example 2 is that:
(II) reducing the porosity of the solid electrolyte layer
And (4) carrying out cold isostatic pressing treatment on the dried electrolyte layer. The hydraulic pressure is 700MPa, the hydraulic time is 5 minutes, the temperature is 20 ℃, specifically, the solid electrolyte layer is placed in the composite film and vacuumized, then the composite film is placed in a cold isostatic pressing device of a wet bag method, the compaction treatment is carried out at the pressure of 700MPa, the hydraulic time is 5 minutes, and the electrode solid electrolyte layer is taken out.
Example 4
The difference from example 2 is that:
(II) reducing the porosity of the solid electrolyte layer
And hot isostatic pressing the dried electrolyte layer. And (3) putting the solid electrolyte layer in the composite film, vacuumizing the composite film, putting the composite film in a cold isostatic pressing device of a wet bag method, compacting the composite film at the pressure of 400MPa for 15 minutes, and taking out the solid electrolyte layer of the electrode, wherein the hydraulic pressure is 400MPa, the hydraulic time is 15 minutes, and the temperature is 75 ℃.
Comparative example 3
(II) reducing the porosity of the solid electrolyte layer
And (4) carrying out cold isostatic pressing treatment on the dried electrolyte layer. The hydraulic pressure is 800MPa, the hydraulic time is 20 minutes, the temperature is 20 ℃, specifically, the solid electrolyte layer is placed in the composite film and vacuumized, then the composite film is placed in a cold isostatic pressing device of a wet bag method, compaction treatment is carried out at the pressure of 800MPa, the hydraulic time is 20 minutes, and the electrode solid electrolyte layer is taken out.
Comparative example 4
The difference from example 2 is that:
(II) reducing the porosity of the solid electrolyte layer
And (4) carrying out cold isostatic pressing treatment on the dried electrolyte layer. The hydraulic pressure is 1MPa, the hydraulic time is 20 minutes, the temperature is 20 ℃, specifically, the solid electrolyte layer is placed in the composite film and vacuumized, then the composite film is placed in a cold isostatic pressing device of a wet bag method, compaction treatment is carried out at the pressure of 1MPa, the hydraulic time is 20 minutes, and the electrode solid electrolyte layer is taken out.
Comparative example 5
The difference from example 2 is that:
(II) reducing the porosity of the solid electrolyte layer
And (4) carrying out cold isostatic pressing treatment on the dried electrolyte layer. And (3) putting the solid electrolyte layer in the composite film, vacuumizing the composite film, putting the composite film in a cold isostatic pressing device adopting a wet bag method, compacting the composite film at the pressure of 350MPa for 20 minutes, and taking out the solid electrolyte layer of the electrode, wherein the hydraulic pressure is 350MPa, the hydraulic time is 20 minutes, and the temperature is 0 ℃.
Comparative example 6
The difference from example 2 is that:
(II) reducing the porosity of the solid electrolyte layer
And carrying out hot isostatic pressing treatment on the dried electrolyte layer. And (3) putting the solid electrolyte layer in the composite film, vacuumizing the composite film, putting the composite film in a cold isostatic pressing device of a wet bag method, compacting the composite film at the pressure of 350MPa for 20 minutes, and taking out the solid electrolyte layer of the electrode, wherein the hydraulic pressure is 350MPa, the hydraulic time is 20 minutes, and the temperature is 200 ℃.
Evaluation of electrode solid electrolyte layers obtained in examples 3 to 4 and comparative examples 3 to 6
3.1, observing the surface morphology of the electrode solid electrolyte layers obtained in the examples 3-4 and the comparative examples 3-6, and testing the porosity of the electrode solid electrolyte layers obtained in the examples 3-4 and the comparative examples 3-6 by using a mercury intrusion instrument, wherein the results are shown in Table 1.
3.2, impedance performance tests are carried out on the electrode solid electrolyte layers obtained in the examples 3-4 and the comparative examples 3-6 by adopting an alternating current impedance meter, and the test results are shown in fig. 9 and fig. 10.
TABLE 1 porosity and surface structure of solid electrolyte layer of examples 2 to 4 and comparative examples 2 to 6
| Examples/comparative examples | Porosity factor | Surface structure of solid electrolyte layer |
| Comparative example 2 | 32.5％ | Smooth surface without obvious wrinkles and deformation |
| Example 2 | 15.2％ | Smooth surface, no wrinkle and no deformation |
| Example 3 | 10.6％ | Smooth surface, no wrinkle and no deformation |
| Example 4 | 12.4％ | Smooth surface, no wrinkle and no deformation |
| Comparative example 3 | 9.3％ | Poor surface flatness and deformation |
| Comparative example 4 | 46.7％ | Smooth surface, no wrinkle and no deformation |
| Comparative example 5 | 17.6％ | Smooth surface, no wrinkle and no deformation |
| Comparative example 6 | 11.3％ | Poor surface flatness and deformation |
As can be seen from table 1, the porosity of the solid electrolyte layers obtained in examples 3 to 4, comparative examples 3 and comparative examples 5 to 6 is significantly smaller than that of the solid electrolyte layer obtained in comparative example 2, while the porosity of the solid electrolyte layer obtained in comparative example 4 is larger than that of the solid electrolyte layer obtained in comparative example 2, and is not much different from that of the solid electrolyte layer which is not compacted; the solid electrolyte layers obtained in examples 3-4 and comparative examples 4-5 have smooth surfaces and no wrinkles and no deformation, while the solid electrolyte layers obtained in comparative example 3 and comparative example 6 have poor smoothness and no deformation, and as can be seen from the combination of examples 2-4 and comparative examples 2-6, the porosity of the solid electrolyte layer can be reduced by increasing the temperature and pressure of the isostatic compaction treatment within a certain range, and the compaction effect of the solid electrolyte layer is not obvious when the pressure of the isostatic compaction treatment is too low.
As can be seen from fig. 9, the impedance of example 3 is greater than that of example 2 and less than that of comparative example 2, and the impedance of example 4 is less than that of example 2, and as can be seen from fig. 10, the impedances of comparative examples 3, 4 and 6 are all significantly greater than those of comparative examples 2 and 2, and the impedance of comparative example 5 is greater than that of comparative example 2 and significantly less than that of example 2, and it is known from the combination of examples 2 to 4 and comparative examples 2 to 6 that increasing the temperature and pressure of the isostatic compaction treatment within a certain range can reduce the impedance of the solid electrolyte layer, but the pressure or temperature of the isostatic compaction treatment is excessively high, which in turn significantly increases the impedance of the solid electrolyte layer. Further, it is understood from the combination of example 2 and comparative examples 2 and 5 that when the hydraulic pressure is sufficiently high, the reduction of the temperature of the isostatic compaction treatment does not significantly reduce the porosity of the solid electrolyte layer, although the effect on the reduction of the resistance is not significant, so that the temperature of the isostatic compaction treatment is preferably not lower than 20 ℃.
In summary, the porosity and resistance of the electrolyte layer can be reduced by properly increasing the temperature and pressure of the isostatic pressing treatment, but too high pressure and temperature can increase the resistance and decrease the conductivity of the solid electrolyte layer, while too low pressure and temperature cannot achieve the effects of better compaction and significantly increasing the conductivity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (15)
1. A method of reducing porosity of a solid state electrolyte layer, comprising: carrying out isostatic compaction treatment on the solid electrolyte layer after film formation and drying;
carrying out first rolling treatment on the film-formed and dried solid electrolyte layer by using rolling equipment in advance before carrying out isostatic pressing treatment;
carrying out second rolling treatment on the isostatic-pressing compacted solid electrolyte layer by using rolling equipment;
the first roll compaction treatment reduces the porosity of the solid electrolyte layer by no more than 25% of the porosity of the solid electrolyte layer reduced by the isostatic compaction treatment,
the second rolling treatment reduces the porosity of the solid electrolyte layer by no more than 25% of the porosity of the solid electrolyte layer reduced by the isostatic pressing treatment;
the pressure of the isostatic compaction treatment is 3-700 MPa, the temperature is 20-150 ℃, and the time is 0.5-180 min;
the isostatic compaction process comprises:
(1) placing the solid electrolyte layer subjected to the first rolling treatment in a sealed elastic die;
(2) and carrying out isostatic compaction treatment on the sealed elastic die by using a liquid medium or a gaseous medium.
2. The method of claim 1, wherein the liquid medium is hydraulic oil or water.
3. The method of claim 1, wherein the isostatic compaction process is a cold isostatic compaction process or a hot isostatic compaction process.
4. The method according to claim 1, wherein the equipment used for the isostatic compaction process is a cold isostatic press or an isostatic press with heating and temperature control functions.
5. The method of claim 4, wherein the cold isostatic press is a wet bag cold isostatic press or a dry bag cold isostatic press.
6. The method of claim 1, wherein the solid electrolyte layer is a self-supporting structure or a composite support structure with a support.
7. The method of claim 1, wherein the solid electrolyte layer comprises a solid electrolyte material, a binder, and an ionic conductor.
8. The method of claim 1, wherein the solid electrolyte layer comprises a solid electrolyte material, a binder, an ionic conductor, a polymeric support, and/or a non-polymeric support.
9. The method according to claim 7, characterized in that the solid state electrolyte material is at least one selected from a sulfide electrolyte, a halogen electrolyte, and an oxide electrolyte.
10. A solid electrolyte layer obtained by the method according to any one of claims 1 to 9.
11. The solid electrolyte layer of claim 10, wherein the solid electrolyte layer has a porosity of 2 to 50%.
12. The solid electrolyte layer of claim 10 wherein the solid electrolyte layer has a porosity of 2 to 25%.
13. Solid state electrolyte layer according to claim 11, characterized in that the conductivity of the solid state electrolyte layer is 10 -6 ~10 -2 S/cm。
14. A battery comprising the solid electrolyte layer according to claim 10 or 11 or the solid electrolyte layer produced by the method according to any one of claims 1 to 9.
15. A vehicle characterized by having the battery of claim 14.
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| CN111933890B (en) * | 2020-07-23 | 2021-10-26 | 蜂巢能源科技有限公司 | All-solid-state battery electrode piece with low porosity and preparation method and application thereof |
| CN112366288A (en) * | 2020-10-30 | 2021-02-12 | 蜂巢能源科技(无锡)有限公司 | Electrolyte membrane, preparation method and application thereof |
| CN112599846B (en) * | 2020-12-24 | 2022-12-09 | 蜂巢能源科技有限公司 | Composite electrolyte membrane for all-solid-state lithium metal negative electrode battery, preparation method of composite electrolyte membrane and all-solid-state sulfide lithium ion battery comprising composite electrolyte membrane |
| CN113517421B (en) * | 2021-07-12 | 2022-06-21 | 四川无量智慧道桥科技有限公司 | Lithium battery pole piece die forming and die casting system and die casting process |
| KR20230097782A (en) * | 2021-12-24 | 2023-07-03 | 주식회사 엘지에너지솔루션 | All-Solid-State Battery Comprising two types of Solid Electrolyte layers and Method for Manufacturing the Same |
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