CN112786839A - Positive plate for solid-state battery and preparation method and application thereof - Google Patents
Positive plate for solid-state battery and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention provides a positive plate for a solid-state battery and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) coating the first slurry on a first current collector, drying and rolling, and forming a first active layer on the first current collector to obtain a first precursor; (2) coating the second slurry on a second current collector, drying, rolling, and forming a second active layer on the second current collector to obtain a second precursor; (3) attaching the first active layer of the first precursor and the second active layer of the second precursor obtained in the step (1) to each other, and removing the second current collector after warm isostatic pressure transfer to obtain the positive plate for the solid-state battery; the first active layer and the second active layer both contain an inorganic solid electrolyte therein. The positive plate for the solid-state battery prepared by the preparation method has higher rate performance and mechanical strength, effectively controls the layered distribution of the binder and the conductive agent, and is beneficial to promoting the commercial application of the all-solid-state battery.
Description
Technical Field
The invention belongs to the field of solid-state batteries, and relates to a positive plate for a solid-state battery, and a preparation method 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, and the synchronous improvement of energy density is realized. Among various new battery systems, solid-state batteries are the next-generation technology closest to the industry, which has become a consensus of the industry and the scientific community. Among them, sulfide electrolytes have relatively high lithium ion conductivity.
However, when the sulfide solid electrolyte is adopted to prepare the all-solid-state electric core system, because the system is not infiltrated by the electrolyte like a liquid battery, the ion migration is totally dependent on the solid electrolyte, therefore, the positive plate must contain electrolyte to ensure the migration of lithium ions, so that compared with the traditional liquid battery plate, the positive plate occupies the proportion of other components, because the sulfide electrolyte belongs to ceramic materials, the adhesive force between particles is poor, the shape is irregular, the density is lower than that of active materials, therefore, the conductivity of the pole piece can be reduced, the porosity can be increased, the thickness of the pole piece can be increased due to the solid electrolyte contained in the positive pole piece with the same surface capacity, this further increases the migration path of lithium ions, resulting in an increase in the internal resistance of the battery, a decrease in rate capability, these are disadvantageous in terms of high performance, long life, and high energy density characteristics sought for all-solid-state batteries.
CN111864205A discloses a positive pole piece of a sulfide solid-state battery and the sulfide solid-state battery. The positive pole piece of the sulfide solid-state battery comprises a positive current collector and a positive active substance layer arranged on at least one surface of the positive current collector, wherein the positive active substance layer comprises a positive active material, a solid electrolyte and an additive salt, and the additive salt is subjected to heat absorption phase change at 40-150 ℃. The sulfide solid-state battery comprising the positive pole piece is also provided. The additive salt which absorbs heat and changes phase at 40-150 ℃ is added into the positive pole piece of the sulfide solid-state battery, and the heat generated in exothermic processes such as self decomposition, side reaction and the like of sulfide solid-state electrolyte in the positive pole piece can be absorbed by using the phase change heat absorption effect of the additive salt in the charging and discharging processes of the battery, so that the thermal runaway risk caused by the rapid rise of the temperature of the battery is reduced, and the thermal safety and the cycle stability of a sulfide solid-state battery system are improved. However, the sulfide solid-state battery has low peel strength and is easily delaminated from the current collector.
CN110336085A discloses a method for weakening internal resistance of a sulfide electrolyte solid-state battery, which comprises a positive electrode layer, a sulfide solid electrolyte layer and a negative electrode layer, which are sequentially stacked; and the positive electrode fusion layer and the negative electrode fusion layer are SEI films formed after the sulfide solid electrolyte layer and the positive electrode layer/the negative electrode layer are subjected to interface reaction under the environment of 6-15V voltage and/or 0.01-0.2C current. But the porosity of the sulfide solid-state battery is high, and the rate capability of the pole piece is reduced.
The above scheme has the problems of low peel strength or low conductivity of the electrode plate, so it is necessary to develop a positive electrode plate for a solid-state battery with high peel strength and good rate capability.
Disclosure of Invention
The invention aims to provide a positive plate for a solid-state battery and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) coating the first slurry on a first current collector, drying and rolling, and forming a first active layer on the first current collector to obtain a first precursor; (2) coating the second slurry on a second current collector, drying, rolling, and forming a second active layer on the second current collector to obtain a second precursor; (3) attaching the first active layer of the first precursor and the second active layer of the second precursor obtained in the step (1) to each other, and removing the second current collector after warm isostatic pressure transfer to obtain the positive plate for the solid-state battery; the first active layer and the second active layer both contain an inorganic solid electrolyte therein. The positive plate for the solid-state battery prepared by the preparation method has higher rate performance and mechanical strength, effectively controls the layered distribution of the binder and the conductive agent, and is beneficial to promoting the commercial application of the all-solid-state battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a positive electrode sheet for a solid-state battery, the method comprising the steps of:
(1) coating the first slurry on a first current collector, drying and rolling, and forming a first active layer on the first current collector to obtain a first precursor;
(2) coating the second slurry on a second current collector, drying, rolling, and forming a second active layer on the second current collector to obtain a second precursor;
(3) attaching the first active layer of the first precursor and the second active layer of the second precursor obtained in the step (1) to each other, and removing the second current collector after warm isostatic pressure transfer to obtain the positive plate for the solid-state battery;
the first active layer and the second active layer both contain an inorganic solid electrolyte therein.
In the method, the preparation sequence of the step (1) and the step (2) is not divided into sequence.
In the preparation method provided by the invention, the first active layer is mainly used for increasing the bonding strength and the conductive ion capacity of the active layer and the current collector, and the second active layer is mainly used for providing the ion conduction capacity. The process characteristics of the transfer compounding of the first active layer and the second active layer are combined, so that the preparation efficiency can be improved, and the cost of the process and materials can be reduced.
Preferably, the inorganic solid-state electrolyte comprises an oxide solid-state electrolyte and/or a sulfide solid-state electrolyte, preferably a sulfide solid-state electrolyte.
Preferably, the sulfide solid electrolyte comprises thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2Or Li2S-B2S3Any one or a combination of at least two of them.
Preferably, the first slurry of step (1) and the second slurry of step (2) each include an active material, a conductive agent, a binder, an inorganic solid electrolyte, and a solvent.
The active materials, the conductive agent, the binder, the electrolyte, the solvent and the like used for preparing the first active layer and the second active layer are preferably selected from the same material, and different materials can be selected according to factors such as cost, performance and the like.
Preferably, in the first slurry, the mass ratio of the active material, the conductive agent, the binder and the inorganic solid electrolyte is (70-90): 4-10): 3-10: (3-10), such as: 70:4:3:3, 90:10:10:10, 75:8:9:7, 80:6:7:8, or 85:6:6:6, etc.
Preferably, in the second slurry, the mass ratio of the active material, the conductive agent, the binder and the inorganic solid electrolyte is (45-70): (0.5-2): 1-3): 25-50), such as: 45:0.5:2:28, 50:0.8:2:29, 60:0.9:1.5:30, 60:1.5:2:40, or 70:2:3:45, etc.
In the invention, the ratio of the binder to the active substance in the first slurry is larger, so that the bonding strength and the electron conductivity of the active layer and the current collector can be improved, and the ratio of the inorganic solid electrolyte in the second slurry is larger, so that the ion conductivity of the pole piece can be improved.
Preferably, the active material comprises LiNixCoyMzO2And an ion conductor coating layer, wherein M includes any one or a combination of at least two of Mn, Al, Zr, Ti, V, Mg, Fe, or Mo, 0. ltoreq. x < 1, for example: 0. 0.1, 0.3, 0.5, 0.7, 0.8, or 0.9, etc., 0 ≦ y < 1, such as: 0. 0.1, 0.3, 0.5, 0.7, 0.8, or 0.9, etc., 0. ltoreq. z < 1, e.g.: 0. 0.1, 0.3, 0.5, 0.7, 0.8, 0.9, etc., and x + y + z is 1.
Preferably, the ion conductor coating layer has a thickness of 1 to 10nm, for example, 1nm, 2nm, 3nm, 4nm, 5nm, 8nm, or 10 nm.
Preferably, the ion conductor coatingThe layer comprises Li2TiO3、LiNbO3、Li3BO3、Li2ZrO3、LiCoO3、LiPO3、Li2MnO4、Al(PO3)3、La(PO3)3Or NaPO3Any one or a combination of at least two of them.
Preferably, the conductive agent includes any one of a zero-dimensional conductive agent, a one-dimensional conductive agent, or a two-dimensional conductive agent, or a combination of at least two thereof.
Preferably, the zero-dimensional conductive agent includes conductive carbon black (SP) and/or Acetylene Black (AB).
Preferably, the one-dimensional conductive agent includes Carbon Nanotubes (CNTs) and/or Vapor Grown Carbon Fibers (VGCF).
Preferably, the two-dimensional conductive agent includes graphene.
Preferably, the binder comprises any one or a combination of at least two of PVDF5130, PVDF75130, PVDF21216, PVDF6020, PVDF-HVS900, PVDF-HFP, PVDF-LBG, NBR, HNBR, SBR, SBS, SEBS, PTEF or PEO.
Preferably, the molecular weight of the binder is 20 to 500 ten thousand, for example: 20, 30, 50, 100, 200, 300, 500, etc.
Preferably, the solvent includes any one or a combination of at least two of dichloromethane, tetrahydrofuran, n-hexane, n-heptane, toluene, 2, 4-dimethyl-3-pentanone, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane, or methylformamide.
Preferably, the solid content of the first slurry in the step (1) is more than or equal to 70 percent, for example: 70%, 72%, 75%, 80%, 85%, or 90%, etc.
Preferably, the solid content of the second slurry in the step (2) is 50-70%, for example: 50%, 52%, 55%, 58%, 60%, 63%, 67%, 70%, or the like.
Preferably, the thickness of the first active layer in the step (1) is 5 to 30 μm, for example: 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, or the like.
Preferably, the first current collector of step (1) comprises a carbon-coated aluminum foil.
Preferably, the thickness of the second active layer in the step (2) is 20 to 150 μm, for example: 20 μm, 50 μm, 80 μm, 100 μm, 150 μm, or the like.
Preferably, the second current collector of step (2) includes, but is not limited to, aluminum foil.
In the invention, the first active layer mainly increases the bonding strength and the electron conductivity of the active layer and the current collector, has low thickness, can increase the stripping force of the pole piece when used as a buffer layer, and the second active layer mainly provides the ion conductivity, has large thickness and can increase the multiplying power performance of the pole piece.
Preferably, the rolling temperature of step (1) and step (2) is independently 40 to 100 ℃, for example: 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C or 100 deg.C.
Preferably, the temperature of the warm isostatic pressing transfer in the step (2) is 30-120 ℃, for example: 30 ℃, 50 ℃, 80 ℃, 100 ℃ or 120 ℃, preferably 40-100 ℃.
Preferably, the pressure of the warm isostatic pressing transfer is 5-700 Mpa, for example: 5MPa, 10MPa, 20MPa, 80MPa, 100MPa, 300MPa, 500MPa or 700MPa, preferably 200-500 MPa.
Preferably, the time of the warm isostatic pressing transfer is 1-720 min, for example: 1min, 10min, 50min, 100min, 500min or 720min, preferably 10-60 min.
Preferably, the pressing times of the warm isostatic pressing transfer are 1-5 times, such as: 1, 2, 3, 4 or 5 times, etc.
Preferably, the total thickness of the first active layer and the second active layer after the warm isostatic pressure transfer is 20 to 100 μm, for example: 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, or the like.
The active material layer of the positive pole piece is low in thickness, and the migration path of lithium ions can be reduced, so that the internal resistance of the battery is reduced, and the cycle performance and the rate performance of the battery are improved.
As a preferable scheme of the invention, the preparation method comprises the following steps:
(1) coating the first slurry on a first current collector, drying and rolling, and forming a first active layer on the first current collector to obtain a first precursor;
(2) coating the second slurry on a second current collector, drying, rolling, and forming a second active layer on the second current collector to obtain a second precursor;
(3) and (2) attaching the first active layer of the first precursor and the second active layer of the second precursor obtained in the step (1) to each other, carrying out temperature isostatic pressure transfer for 1-720 min at 30-120 ℃ and 5-700 Mpa, applying pressure for 1-5 times, and removing the second current collector to obtain the positive plate for the solid-state battery.
In a second aspect, the present invention provides a positive electrode sheet for a solid-state battery, which is produced by the production method according to the first aspect.
In a third aspect, the present invention also provides a solid-state battery comprising the positive electrode sheet for a solid-state battery according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method can effectively control the layered distribution of the binder and the conductive agent, and the arrangement of the first active layer and the second active layer not only ensures the bonding strength of the active layer and the current collector, but also ensures the good electron-conducting capability and ion-conducting capability of the positive plate. The positive plate for the solid-state battery prepared by the preparation method has higher rate performance and mechanical strength, and is beneficial to promoting the commercial application of the all-solid-state battery.
(2) The peel strength of the positive plate for the solid-state battery prepared by the method can reach 13.2N/cm2The multiplying power performance of the 0.5C/0.1C pole piece can reach over 79.1 percent, and the maximum peeling strength can reach 22.5N/cm by controlling the preparation conditions2Above, the multiplying power performance of the 0.5C/0.1C pole piece can reach 93.3%.
Drawings
Fig. 1 is a flow chart of a process for producing a positive electrode sheet for a solid-state battery according to example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a positive plate for a solid-state battery, a flow chart of a preparation process of the positive plate for the solid-state battery is shown in fig. 1, and a specific preparation method is as follows:
(1) taking NCM811@ LiNbO3：Li2S-P2S5: SP: the mass ratio of PVDF21216 is 70: 10:10:10, dissolving PVDF21216 in tetrahydrofuran, wherein the solid content of a glue solution is 6%, stirring, mixing and homogenizing the glue solution and materials of other components to obtain a first slurry with the solid content of 75%, coating the first slurry on a carbon-coated aluminum foil, drying at 80 ℃, and carrying out hot rolling to obtain a first active layer with the thickness of 19 microns;
(2) taking NCM811@ LiNbO3：Li2S-P2S5PVDF21216 in a mass ratio of 55: 40: 2(SP: CNT 3: 7): 3, dissolving PVDF21216 by using tetrahydrofuran, wherein the solid content of the glue solution is 6%, stirring, mixing and homogenizing the glue solution and materials of other components to obtain a second slurry with the solid content of 60%, coating the second slurry on an aluminum foil, drying at 80 ℃, and carrying out hot rolling to obtain a second active layer with the thickness of 88 microns;
(3) and (3) after the two active layers are attached to each other, carrying out temperature isostatic pressure transfer compounding on the two active layers, wherein the transfer conditions are that the temperature is 50 ℃, the pressure is 300MPa, the pressure is applied for 2 times, and the thickness of the active layer of the finished positive plate is 71 microns after removing the aluminum foil on the surface, so that the positive plate for the solid-state battery is obtained.
Example 2
The embodiment provides a positive plate for a solid-state battery, and the preparation method of the positive plate for the solid-state battery comprises the following steps:
(1) taking NCM811@ LiTiO3: LSPCl: (SP: CNT): the mass ratio of PVDF to HFP is 85: 5: 5 (SP: CNT 9: 1): 5 for standby, then using dichloromethane to dissolve PVDF-HFP, the solid content of the glue solution is 5.5 percent, and mixing the glue solution and the glue solutionStirring, mixing and homogenizing materials of the components to obtain a first slurry with the solid content of 78%, coating the first slurry on a carbon-coated aluminum foil, drying at 80 ℃, and carrying out hot rolling to obtain a first active layer with the thickness of 15 microns;
(2) taking NCM811@ LiNbO3: LSPCl (AB: VGCF) and PVDF21216 in a mass ratio of 45: 50: 2 (AB: VGCF ═ 3: 7): 3, dissolving PVDF21216 by using tetrahydrofuran, wherein the solid content of the glue solution is 6%, stirring, mixing and homogenizing the glue solution and materials of other components to obtain a second slurry with the solid content of 63%, coating the second slurry on an aluminum foil, drying at 80 ℃, and carrying out hot rolling to obtain a second active layer with the thickness of 91 microns;
(3) and (3) after the two active layers are attached to each other, carrying out temperature isostatic pressure transfer compounding on the two active layers, wherein the transfer conditions are that the temperature is 60 ℃, the pressure is 400MPa, the pressure is applied for 3 times, and removing the aluminum foil on the surface to obtain a finished product of the positive plate, wherein the thickness of the active layer of the positive plate is 76 microns, so that the positive plate for the solid-state battery is obtained.
Example 3
The embodiment provides a positive plate for a solid-state battery, and the preparation method of the positive plate for the solid-state battery comprises the following steps:
(1) taking NCM811@ LiZrO3: LGPS: (SP: VGCF): the SBS mass ratio is 90: 3:4 (SP: VGCF ═ 8: 2): 3, dissolving SBS by using dimethylbenzene, wherein the solid content of the glue solution is 6.5%, stirring, mixing and homogenizing the glue solution and materials of other components to obtain a first slurry with the solid content of 77%, coating the first slurry on a carbon-coated aluminum foil, drying at 80 ℃, and carrying out hot rolling to obtain a first active layer with the thickness of 10 microns;
(2) taking NCM811@ LiNbO3: the mass ratio of LSPCl (AB: VGCF: graphene) to PVDF-LBG is 66: 31: 2 (AB: VGCF: graphene ═ 3:5: 2): 1, dissolving PVDF-LBG by using tetrahydrofuran, wherein the solid content of a glue solution is 6%, stirring, mixing and homogenizing the glue solution and materials of other components to obtain a second slurry with the solid content of 65%, coating the second slurry on an aluminum foil, drying at 80 ℃, and carrying out hot rolling to obtain a second active layer with the thickness of 79 microns;
(3) and (3) after the two active layers are attached to each other, carrying out temperature isostatic pressure transfer compounding on the two active layers, wherein the transfer conditions are that the temperature is 60 ℃, the pressure is 600MPa, the pressure is applied for 2 times, and the thickness of the active layer of the finished positive plate is 69 micrometers after removing the aluminum foil on the surface, so that the positive plate for the solid-state battery is obtained.
Example 4
The difference between this example and example 1 is only that the temperature for the warm isostatic pressing transfer in step (3) is 30 ℃, the other conditions and parameters are exactly the same as those in example 1, and the thickness of the active layer of the finished positive plate is 75 μm, so as to obtain the positive plate for the solid-state battery.
Example 5
The difference between the present example and example 1 is only that the temperature of the warm isostatic pressing transfer in step (3) is 120 ℃, the other conditions and parameters are exactly the same as those in example 1, and the thickness of the active layer of the finished positive plate is 69.5 μm, so as to obtain the positive plate for the solid-state battery.
Example 6
The difference between this example and example 1 is only that the temperature for the warm isostatic pressing transfer in step (3) is 25 ℃, the other conditions and parameters are exactly the same as those in example 1, and the thickness of the active layer of the finished positive plate is 77 μm, so as to obtain the positive plate for the solid-state battery.
Example 7
The difference between this example and example 1 is only that the temperature for the warm isostatic pressing transfer in step (3) is 130 ℃, the other conditions and parameters are exactly the same as those in example 1, and the thickness of the active layer of the finished positive plate is 68 μm, so as to obtain the positive plate for the solid-state battery.
Example 8
The difference between this example and example 1 is only that the pressure of the warm isostatic pressing transfer in step (3) is 5Mpa, and other conditions and parameters are exactly the same as those in example 1, so as to obtain a finished positive plate with an active layer thickness of 91 μm, and obtain the positive plate for a solid-state battery.
Example 9
The difference between this example and example 1 is only that the pressure of the warm isostatic pressing transfer in step (3) is 700Mpa, and other conditions and parameters are exactly the same as those in example 1, so as to obtain a finished positive plate with an active layer thickness of 69 μm, and obtain the positive plate for the solid-state battery.
Example 10
The difference between this example and example 1 is only that the pressure of the warm isostatic pressing transfer in step (3) is 3Mpa, and other conditions and parameters are exactly the same as those in example 1, so as to obtain a finished positive plate with an active layer thickness of 93 μm, and obtain the positive plate for the solid-state battery.
Example 11
The difference between this example and example 1 is only that the pressure of the warm isostatic pressing transfer in step (3) is 720Mpa, and other conditions and parameters are exactly the same as those in example 1, so as to obtain a finished positive plate with an active layer thickness of 69 μm, and obtain the positive plate for the solid-state battery.
Comparative example 1
The comparative example provides a positive plate, and the preparation method thereof comprises the following steps:
taking NCM811@ Li2ZrO3: LGPS: (SP: CNT): the SBS mass ratio is 60: 32: 4 (SP: VGCF ═ 8: 2): 4, dissolving SBS by using dimethylbenzene, wherein the solid content of the glue solution is 7%, stirring, mixing and homogenizing the glue solution and materials of other components, coating the mixture on a carbon-coated aluminum foil, drying at 80 ℃, and carrying out hot rolling to obtain an active layer with the thickness of 110 microns.
Comparative example 2
The comparative example provides a positive plate, and the preparation method thereof comprises the following steps:
(1) taking NCM811@ Li2NbO3: LGPCl: (SP: VGCF: graphene): the mass ratio of PVDF21216 is 50: 40: 5 (SP: VGCF: graphene ═ 4:4: 2): 5, dissolving PVDF21216 by using cyclohexanone, wherein the solid content of a glue solution is 5.5%, stirring, mixing and homogenizing the glue solution and materials of other components, coating the mixture on a carbon-coated aluminum foil, drying and rolling the mixture at 80 ℃, and obtaining an active layer with the thickness of 112 microns;
(2) and (3) carrying out temperature isostatic pressing treatment on the prepared positive plate, wherein the temperature is 60 ℃, the pressure is 450MPa, and the pressure is applied for three times, so that the thickness of the active layer of the finished positive plate is 88 mu m.
And (3) performance testing:
the positive electrode sheets obtained in examples 1 to 11 and comparative examples 1 to 2 were subjected to a test for peel strength using a vertical peel method; the full solid-state die battery was assembled with the electrolyte layer as a dry powder pellet and the negative electrode as lithium indium, and the rate performance was tested with the test results shown in table 1:
TABLE 1
| Peel strength (N/cm)2) | Gram volume (%)/0.5C/0.1C pole piece | |
| Example 1 | 18.5 | 93.3 |
| Example 2 | 21 | 91.9 |
| Example 3 | 19.5 | 92.5 |
| Example 4 | 17.6 | 89.9 |
| Example 5 | 20.7 | 88.5 |
| Example 6 | 15.9 | 80.1 |
| Example 7 | 17.9 | 82.2 |
| Example 8 | 15.6 | 81.3 |
| Example 9 | 22.5 | 87.5 |
| Example 10 | 13.2 | 79.1 |
| Example 11 | 23.1 | 83.9 |
| Comparative example 1 | 5.9 | 55.1 |
| Comparative example 2 | 12.8 | 75.6 |
As can be seen from Table 1, the peel strength of the positive electrode sheet for solid-state battery prepared by the method of the present invention, as obtained in examples 1 to 11, was 13.2N/cm2The multiplying power performance of the 0.5C/0.1C pole piece can reach over 79.1 percent, and the maximum peeling strength can reach 22.5N/cm by controlling the preparation conditions2Above, the multiplying power performance of the 0.5C/0.1C pole piece can reach 93.3%.
Compared with the examples 4 to 7, the temperature of the temperature and pressure equal-pressure transfer in the step (3) can affect the performance of the prepared positive plate for the solid-state battery, when the temperature is lower than 30 ℃, the binder of the two active layers does not soften, the composite effect is poor, the interfacial impedance can be generated, the resistance modulus of the active layer of the plate is large, the active layer is difficult to compact under lower pressure, and the active layer is damaged under higher pressure. If the temperature is higher than 120 ℃, the softening degree of the binder is too high, the binding power is difficult to maintain, the microstructure of the active layer of the pole piece is damaged, and the performance of the pole piece is poor.
Compared with the examples 8 to 11, the pressure of the temperature isostatic pressing transfer in the step (3) can affect the performance of the prepared positive plate for the solid-state battery, if the pressure is less than 5Mpa, the pressure is too low to play a role in compounding and generate interfacial impedance, and if the pressure is more than 700Mpa, the excessive pressure can cause the binder in the positive plate to lose efficacy and can also cause the active material particles to be damaged and broken, thereby causing the performance of the positive plate to be reduced.
Compared with the comparative examples 1 and 2, the double-layer active layer structure disclosed by the invention has the advantages that the self-advantages of each layer are exerted, and the vertical peeling strength and the rate capability of the sulfide positive plate are improved by combining the warm isostatic pressing treatment process.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a positive plate for a solid-state battery is characterized by comprising the following steps:
(1) coating the first slurry on a first current collector, drying and rolling, and forming a first active layer on the first current collector to obtain a first precursor;
(2) coating the second slurry on a second current collector, drying, rolling, and forming a second active layer on the second current collector to obtain a second precursor;
(3) attaching the first active layer of the first precursor obtained in the step (1) and the second active layer of the second precursor obtained in the step (2) to each other, and removing the second current collector after warm isostatic pressure transfer to obtain the positive plate for the solid-state battery;
the first active layer and the second active layer both contain an inorganic solid electrolyte therein.
2. The production method according to claim 1, wherein the inorganic solid electrolyte is a sulfide solid electrolyte;
preferably, the sulfide solid electrolyte comprises thio-LISICON, Li10GeP2S12、Li6PS5Cl、Li10SnP2S12、Li2S-P2S5、Li2S-SiS2Or Li2S-B2S3Any one or a combination of at least two of them.
3. The production method according to claim 1 or 2, wherein the first slurry of step (1) and the second slurry of step (2) each comprise an active material, a conductive agent, a binder, an inorganic solid electrolyte, and a solvent;
preferably, in the first slurry, the mass ratio of the active material, the conductive agent, the binder and the inorganic solid electrolyte is (70-90): 4-10): 3-10: (3-10);
preferably, the mass ratio of the active material, the conductive agent, the binder and the inorganic solid electrolyte in the second slurry is (45-70): (0.5-2): 1-3): 25-50;
preferably, the active material comprises LiNixCoyMzO2And an ion conductor coating layer, wherein M comprises any one or a combination of at least two of Mn, Al, Zr, Ti, V, Mg, Fe and Mo, x is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, z is more than or equal to 0 and less than 1, and x + y + z is 1;
preferably, the thickness of the ion conductor coating layer is 1-10 nm;
preferably, the ion conductor coating comprisesLi2TiO3、LiNbO3、Li3BO3、Li2ZrO3、LiCoO3、LiPO3、Li2MnO4、Al(PO3)3、La(PO3)3Or NaPO3Any one or a combination of at least two of them.
4. The production method according to claim 3, wherein the conductive agent comprises any one of a zero-dimensional conductive agent, a one-dimensional conductive agent, or a two-dimensional conductive agent, or a combination of at least two thereof;
preferably, the zero-dimensional conductive agent comprises conductive carbon black and/or acetylene black;
preferably, the one-dimensional conductive agent includes carbon nanotubes and/or vapor grown carbon fibers;
preferably, the two-dimensional conductive agent includes graphene;
preferably, the binder comprises any one or a combination of at least two of PVDF5130, PVDF75130, PVDF21216, PVDF6020, PVDF-HVS900, PVDF-HFP, PVDF-LBG, NBR, HNBR, SBR, SBS, SEBS, PTEF or PEO;
preferably, the molecular weight of the binder is 20-500 ten thousand;
preferably, the solvent includes any one or a combination of at least two of dichloromethane, tetrahydrofuran, n-hexane, n-heptane, toluene, 2, 4-dimethyl-3-pentanone, monochlorobenzene, xylene, anisole, cyclohexanone, 1,3, 5-trimethylbenzene, n-decane, or methylformamide.
5. The method according to any one of claims 1 to 4, wherein the solid content of the first slurry in the step (1) is 70% or more;
preferably, the solid content of the second slurry in the step (2) is 50-70%.
6. The production method according to any one of claims 1 to 5, wherein the thickness of the first active layer in the step (1) is 5 to 30 μm;
preferably, the first current collector of step (1) comprises a carbon-coated aluminum foil;
preferably, the thickness of the second active layer in the step (2) is 20-150 μm;
preferably, the second current collector of step (2) comprises aluminum foil;
preferably, the rolling temperature of the step (1) and the step (2) is 40-100 ℃ independently.
7. The method according to any one of claims 1 to 6, wherein the temperature of the warm isostatic pressing transfer in step (2) is 30 to 120 ℃, preferably 40 to 100 ℃;
preferably, the pressure of the warm isostatic pressing transfer is 5-700 MPa, preferably 200-500 MPa;
preferably, the time for the warm isostatic pressing transfer is 1-720 min, preferably 10-60 min;
preferably, the pressing times of the warm isostatic pressing transfer are 1-5 times;
preferably, the total thickness of the first active layer and the second active layer after the warm isostatic pressing transfer is 20 to 100 μm.
8. The method of any one of claims 1 to 7, comprising the steps of:
(1) coating the first slurry on a first current collector, drying and rolling, and forming a first active layer on the first current collector to obtain a first precursor;
(2) coating the second slurry on a second current collector, drying, rolling, and forming a second active layer on the second current collector to obtain a second precursor;
(3) and (3) attaching the first active layer of the first precursor obtained in the step (1) and the second active layer of the second precursor obtained in the step (2) to each other, carrying out temperature isostatic pressure transfer for 1-720 min at 30-120 ℃ and 5-700 MPa, pressing for 1-5 times, and removing the second current collector to obtain the positive plate for the solid-state battery.
9. A positive electrode sheet for a solid-state battery, characterized by being produced by the production method according to any one of claims 1 to 8.
10. A solid-state battery comprising the positive electrode sheet for a solid-state battery according to claim 9.
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