CN112635842A - Solid-state battery and processing method thereof - Google Patents
Solid-state battery and processing method thereof Download PDFInfo
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- CN112635842A CN112635842A CN202011552726.8A CN202011552726A CN112635842A CN 112635842 A CN112635842 A CN 112635842A CN 202011552726 A CN202011552726 A CN 202011552726A CN 112635842 A CN112635842 A CN 112635842A
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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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
- H01M10/058—Construction or manufacture
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a solid-state battery and a processing method thereof, wherein the processing method of the solid-state battery comprises the following steps: after the solid-state battery is charged for the first time, the solid-state battery is heated and pressed. The packaged solid-state battery is heated and pressed after being charged, and after being charged, namely when the volume of active substance components expands to the maximum, the battery is compacted by using external pressure, so that all components of the battery can be fully contacted even when the components expand to the maximum; in addition, the position of the inactive substance component is fixed, the situation that the battery component is broken and damaged due to expansion and contraction of the active substance in the circulation process of the battery is avoided, the circulation performance of the battery is further improved, after the solid-state battery is circulated for 80 weeks, the capacity retention rate can reach more than 83%, and when the solid-state battery is discharged to 60% SOC, the impedance is less than 8.1 omega.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a solid-state battery and a processing method thereof.
Background
The solid-state battery adopts non-flammable solid-state battery electrolyte to replace flammable organic liquid electrolyte, so that the safety of a battery system is greatly improved, the high-energy anode and cathode can be better adapted, the weight of the system is reduced, and the synchronous improvement of energy density is realized. Among various new battery systems, solid-state batteries are the closest technology to the industrialization.
Because no liquid is soaked in the solid-state battery, the solid particles are connected together only by solid-solid contact, and only when the solid particles are in close contact, ions and electrons can be smoothly conducted, so that the internal resistance of the solid-state battery is reduced.
However, the active material in the battery pole piece expands and contracts during the charging and discharging process, and the volume of the inactive material is basically kept unchanged during the charging and discharging process, so that the contact between the active material and other solid particles in the solid-state battery is poor; particularly, when an active material with a large volume change is used in the solid-state battery, for example, the volume expansion of the silicon material can reach 300%, which may cause deformation of the electrode sheet and even the solid-state electrolyte layer during the expansion process, thereby generating cracks in the solid-state battery, and finally causing increase of the internal resistance of the battery, decrease of the cycle performance and even failure.
Currently, the volume change of an active material is mainly suppressed by a method of applying pressure to the outside of a battery using a jig during a charge and discharge cycle of the battery, while compressing other inactive material components while the active material undergoes a volume change, thereby maintaining the contact of a solid-solid interface. However, the disadvantages of this approach are as follows: the external pressure that can be applied by the battery holder is limited, typically below 5MPa, which makes the effect of suppressing volume expansion by the battery holder limited; with the increase of the area of the battery, when the battery clamp is required to provide the same pressure, the battery clamp needs to provide higher pressure, so that the battery clamp needs to adopt a material with higher strength, and the manufacturing cost and the manufacturing difficulty are greatly improved; larger, heavier battery clamps can cause a significant reduction in the overall energy density of the battery.
CN111933890A discloses an all-solid-state battery electrode with low porosity, its preparation method and application, the method comprises: (1) contacting a solid-state battery electrode plate with an organic solvent so as to enable the organic solvent to be filled into pores of the solid-state battery electrode plate; (2) compacting the electrode pole piece obtained in the step (1); (3) and (3) drying the electrode plate obtained in the step (2) along with pressure so as to obtain the all-solid-state battery electrode plate with low porosity. The solid-state battery electrode piece treated by the method has the advantages that the porosity is obviously reduced, the compactness of the accumulation among particles is obviously improved, and the transfer of ions is facilitated. But it still has a problem of expansion deformation during the first charge.
CN109786819A discloses an electrolyte composition and a polymer electrolyte membrane as well as a polymer electrolyte and a preparation method thereof and an all-solid battery and a preparation method thereof. The electrolyte composition contains a polymer, a lithium salt, an ionic liquid and a cross-linking agent, and the structure of the polymer is improved, so that the positive electrode and the electrolyte layer of the battery have higher peel strength and proper compacted density, and the specific capacity, the cycle life and the like of the battery are further improved. The invention changes the composition of electrolyte composition to make the battery have higher peeling strength and proper compacted density, and has the defect of complex process.
CN111987345A discloses a method for improving sintering performance of solid lithium battery. The method comprises the following steps: after coating the negative thermal expansion material by using polystyrene, carrying out composite sintering on the obtained particles serving as a pore-forming agent and a solid electrolyte to form a composite electrolyte with three-dimensional pore structures at two ends, respectively injecting positive and negative electrode materials into pores at two ends, and cooling and sintering to ensure that the formed solid battery is uniform and compact. According to the invention, the particles with negative thermal expansion spontaneously expand in the cooling sintering process to extrude the positive and negative electrode materials, so that the contact between the positive and negative electrode materials and the electrolyte and the overall compactness of the materials are effectively improved, and the performance of the battery is improved. It still has the problems of complex process and charging expansion.
The existing solid-state batteries have the problems of insufficient contact of substances inside the batteries and expansion and contraction in the charging and discharging processes, so that the problem that how to make the substances inside the solid-state batteries fully contact and solve the expansion in the charging and discharging processes becomes the problem which needs to be solved urgently at present under the condition of not changing the structure and the composition of the solid-state batteries.
Disclosure of Invention
In view of the defects in the prior art, the present invention provides a solid-state battery and a processing method thereof, which achieve the effect of fixing the position of the inactive material component by performing heating and pressing processes after the solid-state battery is charged for the first time, and prevent the battery from cracking and damaging the battery component due to the expansion and contraction of the active material during the circulation process, thereby improving the circulation performance of the 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 processing a solid-state battery, the method comprising:
after the solid-state battery is charged for the first time, the solid-state battery is heated and pressed.
The solid-state battery is heated and pressed after being charged for the first time, and after charging, namely when the volume of active substance components expands to the maximum, the battery is compacted by using external pressure, so that all components of the battery can be fully contacted even when the components expand to the maximum; and the binder in the battery is softened by raising the temperature while pressurizing, and then is re-solidified after cooling, so that the positions of inactive material components are fixed, the conditions of battery component fracture and damage caused by expansion and contraction of active materials in the circulation process of the battery are prevented, and the circulation performance of the battery is improved.
As a preferred technical solution of the present invention, the processing method specifically includes the steps of:
after the solid-state battery is charged for the first time, the solid-state battery is heated for a certain time, and after heating, the heating temperature is maintained to apply pressure to the solid-state battery.
As a preferable aspect of the present invention, the solid-state battery is charged to 100% SOC for the first time.
When the solid-state battery is charged to 100% SOC, the volume of the active material component expands to the maximum, and the contact effect of the components in the battery can be more effectively improved by applying pressure.
Note that the SOC, i.e., the state of charge, is used to reflect the remaining capacity of the battery, and is numerically defined as the ratio of the remaining capacity to the battery capacity, and is usually expressed as a percentage. The value range is 0-100%, when SOC is 0, the battery is completely discharged, and when SOC is 100%, the battery is completely full.
In a preferred embodiment of the present invention, the heating temperature is 50 to 90 ℃, for example, 50 ℃, 54 ℃, 58 ℃, 62 ℃, 66 ℃, 70 ℃, 74 ℃, 78 ℃, 82 ℃, 86 ℃ or 90 ℃, but the temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
According to the invention, by controlling the heating temperature, substances in the battery are softened without damaging the internal structure of the battery at the temperature of 50-90 ℃, and if the temperature is lower than 50 ℃, the binder cannot be softened and cannot be fully compacted in the pressurizing process; if the temperature is higher than 90 ℃, the fluidity of the binder after softening is too good, which may result in the destruction of the battery structure during the pressurization process.
In a preferred embodiment of the present invention, the heating time is 5 to 30min, for example, 5min, 8min, 11min, 14min, 17min, 20min, 23min, 26min, 29min or 30min, but the heating time is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the pressure applied is 20 to 700MPa, for example, 20MPa, 70MPa, 140MPa, 210MPa, 280MPa, 350MPa, 420MPa, 490MPa, 560MPa, 630MPa or 700MPa, but the pressure is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the pressing time is 3-20 min, for example, 3min, 4min, 6min, 8min, 10min, 12min, 14min, 16min, 18min or 20min, but the pressing time is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
In a preferred embodiment of the present invention, the heating and pressing are followed by cooling and standing at room temperature.
In a preferred embodiment of the present invention, the room temperature is 20 to 30 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but the temperature is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Illustratively, the present invention provides a method for manufacturing a solid-state battery, specifically comprising:
mixing a positive electrode active material, a solid electrolyte, a binder, a conductive agent and a solvent, homogenizing, coating on a positive electrode current collector, and drying slurry to obtain a positive electrode piece; mixing a solid electrolyte, a binder and a solvent, homogenizing, coating on the positive pole piece, and drying to obtain a composite pole piece; mixing a negative electrode active material, a solid electrolyte, a binder, a conductive agent and a solvent, homogenizing, coating on a negative electrode current collector, and drying to obtain a negative electrode plate;
(II) stacking the composite pole piece and the negative pole piece together, and welding a tab and packaging the composite pole piece and the negative pole piece with an aluminum-plastic film to obtain a solid-state battery;
as known to those skilled in the art, the positive electrode plate and the negative electrode plate can be used after being dried and rolled and cut, and those skilled in the art can reasonably process the positive electrode plate and the negative electrode plate according to the use requirements.
It should be noted that the material of the positive electrode active material in the present invention is not specifically required or limited, and those skilled in the art can reasonably select the material of the positive electrode active material according to actual requirements, for example, the positive electrode active material includes one or a combination of at least two of ternary positive electrode material, lithium titanate, lithium iron phosphate, and lithium manganate.
It should be noted that the material of the negative active material in the present invention is not particularly limited, and those skilled in the art can reasonably select the material of the negative active material according to actual needs, for example, the negative active material includes one or a combination of at least two of graphite, silica material, or silicon.
It should be noted that the material of the binder of the present invention is not specifically required or limited, and those skilled in the art can reasonably select the material of the binder according to actual needs, for example, the binder includes styrene butadiene rubber and/or polyvinylidene fluoride.
It should be noted that the material of the conductive agent is not specifically required or limited, and those skilled in the art can reasonably select the material of the conductive agent according to actual needs, for example, the conductive agent includes one or a combination of at least two of ketjen black, acetylene black, and superconducting carbon black.
It should be noted that the material of the solid electrolyte material is not specifically required or limited, and those skilled in the art can reasonably select the material of the conductive agent according to actual needs, for example, the solid electrolyte material includes a sulfide electrolyte, an oxide electrolyte, a halogen electrolyte, an anti-perovskite electrolyte, and the like.
It should be noted that, the invention does not make specific requirements and special limitations on the materials of the positive current collector and the negative current collector, and those skilled in the art can reasonably select the materials of the positive current collector and the negative current collector according to actual requirements, for example, the material of the positive current collector is aluminum foil, and the material of the negative current collector is copper foil.
Illustratively, the invention provides a method for processing a solid-state battery, which specifically comprises:
charging the solid-state battery to 100% SOC for the first time, heating the solid-state battery for 5-30 min at 50-90 ℃ after charging, keeping the heating temperature for applying pressure for 3-20 min at 20-700 MPa after heating, and cooling and standing at room temperature of 20-30 ℃ after applying pressure.
In a second aspect, the present invention provides a solid-state battery treated by the method for treating a solid-state battery according to the first aspect.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
the solid-state battery is heated and pressed after being charged for the first time, and after charging, namely when the volume of active substance components expands to the maximum, the battery is compacted by using external pressure, so that all components of the battery can be fully contacted even when the components expand to the maximum; and the binder in the battery is softened by raising the temperature while pressurizing, and then is re-solidified after cooling, so that the position of the inactive substance component is fixed, the situation that the battery is broken and damaged due to expansion and contraction of the active substance in the circulation process is prevented, the circulation performance of the battery is further improved, the capacity retention rate can reach more than 83% after the solid-state battery is circulated for 80 weeks, and the impedance is less than 8.1 omega when the solid-state battery is discharged to 60% SOC.
Drawings
Fig. 1 is a graph comparing the capacity retention rates of solid-state batteries after treatment in example 1 of the present invention and comparative example 1.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The present embodiment provides a solid-state battery, which is processed by a processing method of the solid-state battery as follows:
charging the solid-state battery to 100% SOC for the first time, heating the solid-state battery for 15min at 60 ℃ after charging, then performing pressure treatment at 300MPa for 10min at 60 ℃, and cooling and standing at room temperature of 20-30 ℃ after pressure treatment.
Example 2
The present embodiment provides a solid-state battery, which is processed by a processing method of the solid-state battery as follows:
charging the solid battery to 100% SOC for the first time, heating the solid battery at 50 deg.C for 30min after charging, applying pressure at 50 deg.C under 20MPa for 20min, cooling at room temperature of 20 deg.C, and standing.
Example 3
The present embodiment provides a solid-state battery, which is processed by a processing method of the solid-state battery as follows:
charging the solid battery to 100% SOC for the first time, heating the solid battery at 90 deg.C for 5min after charging, applying pressure at 200MPa at 90 deg.C for 15min, cooling at room temperature of 30 deg.C, and standing.
Example 4
The present embodiment provides a solid-state battery, which is processed by a processing method of the solid-state battery as follows:
charging the solid battery to 100% SOC for the first time, heating the solid battery at 70 deg.C for 20min after charging, applying pressure at 360MPa at 70 deg.C for 8min, cooling at 28 deg.C after heating and applying pressure, and standing.
Example 5
The present embodiment provides a solid-state battery, which is processed by a processing method of the solid-state battery as follows:
charging the solid battery to 100% SOC for the first time, heating the solid battery at 80 deg.C for 25min, applying pressure at 80 deg.C under 700MPa for 3min, cooling at 26 deg.C, and standing.
Example 6
This example provides a solid-state battery and a method of processing based on the method of processing described in example 1, except that the temperature of heating was 45 ℃, and the remaining operating parameters and steps were exactly the same as in example 1.
Example 7
This example provides a solid-state battery and a method of processing based on the method of processing described in example 1, except that the temperature of heating was 95 ℃, and the remaining operating parameters and steps were exactly the same as in example 1.
Comparative example 1
This comparative example provides a solid-state battery and a method of treating the same, which is a conventional method as compared with example 1, and specifically comprises the following steps:
in the charging process that the solid-state battery is charged to 100% SOC for the first time, the solid-state battery is clamped by a clamp, and the clamping pressure of the clamp is 5 MPa.
Illustratively, there is provided a method of manufacturing a solid-state battery before charging, the method comprising the steps of:
weighing polycrystalline nickel cobalt lithium manganate particles, lithium sulfur chloride phosphate particles, styrene butadiene rubber and Ketjen black according to a mass ratio of 50:48:1:1, mixing with a solvent, homogenizing, coating on an aluminum foil, drying slurry, and performing roll-in cutting to obtain a positive pole piece; weighing lithium sulfochloride particles and polyvinylidene fluoride according to a mass ratio of 95:5, mixing with a solvent, coating on the positive pole piece, and drying to obtain a composite pole piece; weighing silicon, lithium sulfur phosphate particles, polyvinylidene fluoride and Ketjen black according to the mass ratio of 15:80:3:2, mixing with a solvent, coating on a copper foil, drying, and rolling and cutting to obtain a negative pole piece;
and (II) stacking the composite pole piece and the negative pole piece together, and welding a tab and packaging the composite pole piece and the negative pole piece with an aluminum-plastic film to obtain the solid-state battery.
The solid-state battery after being processed is tested for the retention rate of impedance and capacity, and the testing method comprises the following steps:
(1) impedance testing
Discharging the solid-state batteries to 60% of SOC, and carrying out impedance test on the solid-state batteries;
(2) capacity Retention Rate test
The solid-state battery was subjected to a charge-discharge cycle test under conditions of 0.1C magnification and 100% SOC charge-discharge.
The test results are shown in table 1, and fig. 1 is a graph comparing the capacity retention rates of the solid-state batteries after the treatment in example 1 of the present invention and comparative example 1.
TABLE 1
Impedance/omega | Capacity retention after 80 weeks of cycling% | |
Example 1 | 6.9 | 91 |
Example 2 | 7.7 | 85 |
Example 3 | 7.2 | 88 |
Example 4 | 6.7 | 92 |
Examples5 | 6.3 | 95 |
Example 6 | 8.1 | 83 |
Example 7 | 7.8 | 84 |
Comparative example 1 | 8.6 | 82 |
As can be seen from table 1:
(1) compared with the embodiments 6 and 7, the impedance of the embodiment 1 is lower than that of the embodiments 6 and 7, and the capacity retention rate of the embodiment 1 is better than that of the embodiments 6 and 7, so that the invention can be illustrated that substances in the battery are softened without damaging the internal structure of the battery under the temperature range of 50-90 ℃ by controlling the heating temperature, and if the temperature is lower than 50 ℃, the binder cannot be softened, and the binder cannot be fully compacted in the pressurizing process; if the temperature is higher than 90 ℃, the fluidity of the binder after softening is too good, which may result in the destruction of the battery structure during the pressurization process.
(2) Compared with the comparative example 1, the impedance in the example 1 is lower than that in the comparative example 1, and the capacity retention rate of the example 1 is obviously higher than that of the comparative example 1, and by combining with fig. 1, the invention can ensure that the solid electrolyte and the positive active material are tightly stacked, and the damage of an inactive material layer caused by the expansion and contraction of the active material in the subsequent circulation process is relieved, so that the circulation performance of the battery is improved.
(3) From the test results of examples 1 to 7, it can be shown that the present invention enables the components of the battery to be sufficiently contacted even at the time of maximum expansion by subjecting the solid-state battery to a heating and pressing treatment after the initial charge, and compacting the battery using an applied pressure after the charge, that is, when the volume of the active material component expands to the maximum; and the binder in the battery is softened by raising the temperature while pressurizing, and then is re-solidified after cooling, so that the position of the inactive material component is fixed, the situation that the battery is cracked and damaged due to expansion and contraction of the active material in the circulation process is prevented, and the circulation performance of the battery is further improved.
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 method for processing a solid-state battery is characterized by comprising the following steps:
after the solid-state battery is charged for the first time, the solid-state battery is heated and pressed.
2. The processing method according to claim 1, characterized in that the processing method comprises the following steps:
after the solid-state battery is charged for the first time, the solid-state battery is heated for a certain time, and after heating, the heating temperature is maintained to apply pressure to the solid-state battery.
3. The process of claim 2, wherein the solid-state battery is first charged to 100% SOC.
4. The process according to claim 2 or 3, wherein the heating temperature is 50 to 90 ℃.
5. The process according to any one of claims 2 to 4, wherein the fixed time is 5 to 30 min.
6. The process according to any one of claims 2 to 5, wherein the pressure is 20 to 700 MPa.
7. The process according to any one of claims 2 to 6, wherein the pressing time is 3 to 20 min.
8. The process according to any one of claims 2 to 7, wherein the pressure application treatment is followed by a cooling and standing at room temperature.
9. The process according to claim 8, wherein the room temperature is 20 to 30 ℃.
10. A solid-state battery characterized in that the solid-state battery is treated by the method for treating a solid-state battery according to any one of claims 1 to 9.
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