CN111710817A - Solid-state battery and preparation method and application thereof - Google Patents
Solid-state battery and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a solid-state battery and a preparation method and application thereof, wherein the method comprises the following steps: (1) modifying the positive electrode active material particles; (2) applying composite anode slurry mixed by a surface-modified anode material, oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent on the surface of an anode current collector; (3) applying composite negative electrode slurry mixed by a negative electrode material, oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent on the surface of a negative electrode current collector; (4) carrying out heat treatment on the composite positive electrode and the composite negative electrode; (5) applying electrolyte slurry mixed by a first polymer monomer, a second polymer monomer, a photoinitiator and a lithium salt on the surface of the composite positive electrode after heat treatment; (6) applying ceramic slurry mixed by oxide ceramic, a binder, lithium salt and a solvent on the surface of the composite negative electrode after heat treatment; (7) and slicing the composite positive electrode and the composite negative electrode, then alternately overlapping, welding tabs and packaging.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a solid-state battery and a preparation method and application thereof.
Background
Compared with the traditional lithium ion battery, the solid-state battery has the advantages of high safety performance, long cycle life, wide working temperature range and the like. However, the practical application of the all-solid lithium battery is limited due to low conductivity of the solid electrolyte, poor mechanical stability and high electrode/electrolyte interface impedance.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a solid-state battery, a method for manufacturing the same, and applications of the same, by which interfacial impedance between an electrolyte and an electrode can be effectively reduced, and interfacial gap generation can be reduced, so that the obtained solid-state battery has excellent safety and electrical properties.
In one aspect of the invention, a method of making a solid-state battery is presented. According to an embodiment of the invention, the method comprises:
(1) forming a coating layer containing oxide ceramic on the surface of the positive electrode active material particles so as to obtain a surface-modified positive electrode material;
(2) mixing the surface-modified positive electrode material with oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent to prepare composite positive electrode slurry, and applying the composite positive electrode slurry on the surface of a positive electrode current collector to prepare composite positive electrodes with different concentration gradients;
(3) mixing a negative electrode material with oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent to prepare composite negative electrode slurry, and applying the composite negative electrode slurry on the surface of a negative electrode current collector to prepare composite negative electrodes with different concentration gradients;
(4) respectively carrying out heat treatment on the composite positive electrode and the composite negative electrode;
(5) mixing a first polymer monomer, a second polymer monomer, a photoinitiator and lithium salt to prepare electrolyte slurry, applying the electrolyte slurry on the surface of the heat-treated composite positive electrode obtained in the step (4), and then curing;
(6) mixing oxide ceramic, a binder, lithium salt and a solvent to prepare ceramic slurry, applying the ceramic slurry on the surface of the heat-treated composite negative electrode obtained in the step (4), curing, and then performing insulation treatment on the edge of the obtained composite negative electrode;
(7) and (4) slicing the composite positive electrode obtained in the step (5) and the composite negative electrode obtained in the step (7), sequentially and alternately superposing to obtain a battery cell, and welding a lug and packaging after heat treatment of the battery cell to obtain the solid-state battery.
According to the method for preparing the solid-state battery provided by the embodiment of the invention, the surface-modified positive electrode material is obtained by forming the coating layer containing the oxide ceramic on the surface of the positive electrode active material particles, the coating material containing the oxide ceramic has ionic conductivity, and is beneficial to improving the ion transmission rate of active substances in the positive electrode material, simultaneously is beneficial to reducing the thermal decomposition temperature of the active substances and improving the safety, then the surface-modified positive electrode material is mixed with the oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent to prepare the composite positive electrode slurry, and the composite positive electrode slurry is applied to the surface of a positive electrode current collector to prepare composite positive electrodes with different concentration gradients (the concentration gradient of the composite positive electrode slurry is reduced in sequence along the direction away from the positive electrode current collector), so that the uniform distribution of the conductive agent at the inner layer and the outer layer of the active substances of, Relieving the space charge layer effect, simultaneously mixing a negative electrode material with oxide ceramics, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent to prepare composite negative electrode slurry, applying the composite negative electrode slurry on the surface of a negative electrode current collector, preparing composite negative electrodes with different concentration gradients (the concentration gradient of the composite negative electrode slurry is sequentially reduced along the direction far away from the negative electrode current collector), facilitating the uniform distribution of the conductive agent on the inner layer and the outer layer of an active material of a negative electrode sheet and relieving the space charge layer effect, then respectively carrying out heat treatment on the obtained composite positive electrode and the composite negative electrode, then mixing a first polymer monomer, a second polymer monomer, a photoinitiator and the lithium salt to prepare electrolyte slurry, applying the electrolyte slurry on the surface of the obtained heat-treated composite positive electrode and then carrying out solidification so as to form a solid electrolyte diaphragm on the surface of the heat-treated composite positive electrode, mixing oxide ceramic, a binder, lithium salt and a solvent to prepare ceramic slurry, applying the ceramic slurry on the surface of the obtained heat-treated composite negative electrode, and then curing, wherein a ceramic coating plays a role in physically isolating a positive electrode from a negative electrode and simultaneously guaranteeing ion conduction, then performing insulation treatment on the edge of the obtained composite negative electrode, because the size of a battery core laminated positive electrode is smaller than that of the negative electrode, the insulation treatment is performed on the edge of the composite negative electrode, so that short circuit caused by the fact that a current collector on the edge of the positive electrode is burred or an active substance contacts the negative electrode can be prevented, finally, slicing the obtained composite positive electrode and the composite negative electrode, sequentially and alternately overlapping to prepare a battery core, welding a tab after the battery core is subjected to heat treatment. Therefore, by adopting the method, the interface impedance between the electrolyte and the electrode can be effectively reduced, and the generation of interface gaps is reduced, so that the obtained solid-state battery has excellent safety performance and electrical performance.
In addition, the method of manufacturing a solid-state battery according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the present invention, in the step (1), the positive active material particles are at least one selected from the group consisting of ternary 622 positive electrode material particles and ternary 523 positive electrode material particles.
In some embodiments of the present invention, in step (1), the thickness of the coating layer is 0.5 to 10 nm.
In some embodiments of the present invention, in steps (1), (2), (3) and (6), the oxide ceramic is at least one selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium tantalum oxygen and lithium lanthanum zirconium aluminum oxygen.
In some embodiments of the present invention, in steps (2) and (3), the polymer solid electrolyte is at least one selected from the group consisting of polyether polymers, polyamine polymers, polythioether polymers, polyacrylate polymers, and polyacrylonitrile polymers.
In some embodiments of the present invention, in steps (2), (3), (5) and (6), the lithium salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate and lithium dioxalate borate.
In some embodiments of the present invention, in steps (2), (3) and (6), the solvent is at least one selected from the group consisting of N-methylpyrrolidone, dimethylformamide, acetonitrile, ethyl acetate and deionized water.
In some embodiments of the present invention, in the step (2), the mass ratio of the surface-modified cathode material to the oxide ceramic, the lithium salt, the polymer solid electrolyte, the binder, and the conductive agent is (80-96): (1-8): (0.5-3): (1-4): (2-4): (3-8).
In some embodiments of the present invention, in the step (2), the solid content of the composite cathode slurry is 30 to 60 wt%.
In some embodiments of the present invention, in the step (3), the mass ratio of the negative electrode material to the oxide ceramic, the lithium salt, the polymer solid electrolyte, the binder, and the conductive agent is (90 to 96): (0.5-6): (0.5-3): (2-4): (1.5-4): (2.5-8).
In some embodiments of the present invention, in the step (3), the solid content of the composite anode slurry is 30 to 55 wt%.
In some embodiments of the present invention, in the step (4), the temperature of the heat treatment is 80 to 100 ℃, the pressure is 0.1 to 0.8MPa, and the time is 5 to 15 minutes.
In some embodiments of the present invention, in the step (5), the mass ratio of the first polymer monomer, the second polymer monomer, the photoinitiator, and the lithium salt is (10 to 50): (45-80): (0.1-0.5): (1.5-10).
In some embodiments of the present invention, in the step (5), the solid content of the electrolyte slurry is 30 to 55 wt%.
In some embodiments of the present invention, in step (5), the first polymer monomer is polyethylene glycol methyl ether methacrylate, the second polymer monomer is at least one selected from vinylene carbonate and ethylene carbonate, and the photoinitiator is at least one selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone and azobisisobutyronitrile.
In some embodiments of the present invention, in the step (6), the mass ratio of the oxide ceramic, the binder and the lithium salt is (80-95): (3-5): (5-10).
In some embodiments of the present invention, in step (6), the ceramic slurry has a solid content of 40 to 55 wt%.
In a second aspect of the invention, a solid-state battery is provided. According to an embodiment of the present invention, the solid-state battery is prepared by the above method. Thus, the solid-state battery has excellent safety performance and electrical performance.
In a third aspect of the present invention, a vehicle is presented. According to an embodiment of the present invention, the vehicle has the solid-state battery described above. Therefore, the vehicle loaded with the solid-state battery with excellent safety performance and electric performance has excellent driving range.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following described embodiments are exemplary and are intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, a method of making a solid-state battery is presented. According to an embodiment of the invention, the method comprises:
s100: forming a coating layer containing oxide ceramic on the surface of positive electrode active material particles
In this step, a coating layer containing oxide ceramic is formed on the surface of the positive electrode active material particles, to obtain a surface-modified positive electrode material. The inventors found that the coating material containing the oxide ceramic has ionic conductivity, and contributes to increase of ion transport rate of the active material in the positive electrode material, and at the same time, contributes to decrease of thermal decomposition temperature of the active material, and improves safety. According to an embodiment of the present invention, the positive electrode active material particles include, but are not limited to, at least one selected from ternary 622 positive electrode material particles and ternary 523 positive electrode material particles, and the coating layer has a thickness of 0.5 to 10nm, such as 0.5nm, 0.6nm … … 9.9.9 nm, 10 nm. The inventors have found that if the coating layer is too thick, the rate performance of the battery tends to be lowered, and if the coating layer is too thick, the purpose of improving the safety and increasing the ion transport rate cannot be achieved. And the oxide ceramic is at least one selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, lithium titanium aluminum phosphate, lithium germanium aluminum phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium tantalum oxygen, and lithium lanthanum zirconium aluminum oxygen. The manner of forming the coating layer containing the oxide ceramic on the surface of the positive electrode active material in this step is not particularly limited, and those skilled in the art can select the coating layer according to actual needs as long as the above-described effects can be achieved.
S200: mixing the surface-modified positive electrode material with oxide ceramic, lithium salt, polymer solid electrolyte, binder, conductive agent and solvent to prepare composite positive electrode slurry, and applying the composite positive electrode slurry on the surface of a positive electrode current collector
In the step, the obtained surface-modified positive electrode material is mixed with oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent to prepare composite positive electrode slurry, and the composite positive electrode slurry is applied to the surface of a positive electrode current collector to prepare composite positive electrodes with different concentration gradients (the concentration gradients of the composite positive electrode slurry are sequentially reduced along the direction away from the positive electrode current collector), so that the uniform distribution of the conductive agent on the inner layer and the outer layer of an active material of a positive plate is facilitated, and the space charge layer effect is relieved. It should be noted that the manner of preparing the composite positive electrode with different concentration gradients is not particularly limited, and for example, the composite positive electrode can be prepared by multiple coating manners such as extrusion or transfer coating. According to one embodiment of the invention, the mass ratio of the surface modified cathode material to the oxide ceramic, the lithium salt, the polymer solid electrolyte, the binder and the conductive agent is (80-96): (1-8): (0.5-3): (1-4): (2-4): (3-8), for example, the mass ratio is (80, 81 … … 95, 96): (1, 2 to … … 7, 8): (0.5, 0.6 … … 2.9.9, 3): (1, 1.1-3.9, 4): (2, 2.1-3.9, 4): (3, 3.1 to 7.9, 8). The inventor finds that the proportion of the oxide to the polymer electrolyte needs to be proper, if the proportion of the oxide ceramic to the polymer solid electrolyte is too high or too low, the conductivity of the organic-inorganic composite electrolyte is low, the performance of the electrical property is affected, and if the proportion of the oxide ceramic to the polymer solid electrolyte is too low, the problems of coating failure, poor processing performance and the like are caused. Meanwhile, the solid content of the obtained composite cathode slurry is 30-60 wt%, such as 30 wt%, 31 wt% … … 59 wt%, 60 wt%. The inventor finds that if the solid content of the composite anode slurry is too low, coating leakage and coating thickness do not reach the standard easily; and if the solid content of the composite anode slurry is too high, the problems of too thick coating thickness, coating incapability and the like are easily caused.
Further, the oxide ceramic includes, but is not limited to, at least one selected from the group consisting of alumina, silica, titania, lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium tantalum oxygen, and lithium lanthanum zirconium aluminum oxygen; the polymer solid electrolyte includes, but is not limited to, at least one selected from polyether polymers, polyamine polymers, polythioether polymers, polyacrylate polymers, and polyacrylonitrile polymers; the lithium salt includes, but is not limited to, at least one selected from the group consisting of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate and lithium dioxalate borate; the solvent includes, but is not limited to, at least one selected from the group consisting of N-methylpyrrolidone, dimethylformamide, acetonitrile, ethyl acetate, and deionized water; binders include, but are not limited to, at least one of PVDF, PEO, and modacrylic; the conductive agent includes, but is not limited to, at least one of SP, CNT, and mesocarbon microbeads.
S300: mixing a negative electrode material with oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent to prepare composite negative electrode slurry, and applying the composite negative electrode slurry on the surface of a negative electrode current collector
In the step, a negative electrode material is mixed with oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent to prepare composite negative electrode slurry, and the composite negative electrode slurry is applied to the surface of a negative electrode current collector to prepare composite negative electrodes with different concentration gradients (the concentration gradients of the composite negative electrode slurry are sequentially reduced along the direction far away from the negative electrode current collector), so that the uniform distribution of the conductive agent on the inner layer and the outer layer of an active substance of a negative plate is facilitated, and the space charge layer effect is relieved. It should be noted that the manner of preparing the composite negative electrodes with different concentration gradients is not particularly limited, and may be, for example, extrusion or transfer coating multiple times. According to one embodiment of the invention, the mass ratio of the anode material to the oxide ceramic, the lithium salt, the polymer solid electrolyte, the binder and the conductive agent is (90-96): (0.5-6): (0.5-3): (2-4): (1.5-4): (2.5-8), for example, the mass ratio is (90, 90.1-95.9, 96): (0.5, 0.6-5.9, 6): (0.5, 0.6-2.9, 3): (2, 2.1-3.9, 4): (1.5, 1.6-3.9, 4): (2.5, 2.6-7.9, 8). The inventor finds that the proportion of the oxide to the polymer electrolyte needs to be proper, if the proportion of the oxide ceramic to the polymer solid electrolyte is too high or too low, the conductivity of the organic-inorganic composite electrolyte is low, the performance of the electrical property is affected, and if the proportion of the oxide ceramic to the polymer solid electrolyte is too low, the problems of coating failure, poor processing performance and the like are caused. Meanwhile, the solid content of the obtained composite anode slurry is 30-55 wt%, such as 30 wt%, 31 wt% … … 54 wt%, and 55 wt%. The inventor finds that if the solid content of the composite cathode slurry is too low, coating leakage and coating thickness do not reach the standard easily; and if the solid content of the composite cathode slurry is too high, the problems of too thick coating thickness, coating incapability and the like are easily caused.
Further, the anode material includes, but is not limited to, at least one of artificial graphite, natural graphite, soft carbon, and hard carbon, the oxide ceramic includes, but is not limited to, at least one selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, lithium titanium aluminum phosphate, lithium germanium aluminum phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium tantalum oxygen, and lithium lanthanum zirconium aluminum oxygen; the polymer solid electrolyte includes, but is not limited to, at least one selected from polyether polymers, polyamine polymers, polythioether polymers, polyacrylate polymers, and polyacrylonitrile polymers; the lithium salt includes, but is not limited to, at least one selected from the group consisting of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate and lithium dioxalate borate; the solvent includes, but is not limited to, at least one selected from the group consisting of N-methylpyrrolidone, dimethylformamide, acetonitrile, ethyl acetate, and deionized water; binders include, but are not limited to, at least one of PVDF, PEO, and modacrylic; the conductive agent includes, but is not limited to, at least one of SP, CNT, and mesocarbon microbeads.
S400: respectively carrying out heat treatment on the composite positive electrode and the composite negative electrode
In the step, the obtained composite positive electrode and the composite negative electrode are respectively subjected to heat treatment, so that the close contact of the positive electrode, the negative electrode and the middle electrolyte layer is ensured, the interface impedance is reduced, and the electrical performance of the battery is ensured to be exerted. According to an embodiment of the invention, the temperature of the composite positive electrode and the temperature of the composite negative electrode are 80-100 ℃, the pressure is 0.1-0.8 MPa, and the time is 5-15 minutes.
S500: mixing a first polymer monomer, a second polymer monomer, a photoinitiator and a lithium salt to prepare electrolyte slurry, applying the electrolyte slurry on the surface of the heat-treated composite positive electrode obtained in the step S400, and curing
In the step, a first polymer monomer, a second polymer monomer, a photoinitiator and a lithium salt are mixed to prepare an electrolyte slurry, the electrolyte slurry is applied to the surface of the heat-treated composite positive electrode obtained in the step S400 and then cured, and the in-situ polymerization of the polymer monomers is promoted under the induction action of the initiator to form a continuous and compact electrolyte layer. . According to a specific embodiment of the invention, the mass ratio of the first polymer monomer, the second polymer monomer, the photoinitiator and the lithium salt is (10-50): (45-80): (0.1-0.5): (1.5-10), for example, the mass ratio is (10, 11-49, 50): (45, 46-79, 80): (0.1, 0.2, 0.3, 0.4, 0.5): (1.5, 1.6-9.9, 10). The inventors have found that if the initiator content is too high, the polymerization degree tends to be too high, the electrolyte layer after polymerization tends to be too hard, and the conductivity tends to be too low, whereas if the initiator content is too low, the polymerization degree tends to be low or polymerization tends to be impossible. Meanwhile, the solid content of the electrolyte slurry is 30-55 wt%, such as 30 wt%, 31 wt% … … 54 wt%, 55 wt%. The inventor finds that if the solid content of the electrolyte slurry is too low, the coating leakage and the coating thickness do not reach the standard easily; and if the solid content of the electrolyte slurry is too high, the problems of too thick coating thickness, coating incapability and the like are easily caused. Specifically, the curing method is not particularly limited as long as the curing can be achieved, for example, ultraviolet irradiation curing is adopted, and the temperature of the ultraviolet irradiation curing is 25-40 ℃ for 20-120 minutes.
Further, the first polymer monomer includes, but is not limited to, polyethylene glycol methyl ether methacrylate, the second polymer monomer includes, but is not limited to, at least one selected from the group consisting of vinylene carbonate and ethylene carbonate, the photoinitiator includes, but is not limited to, at least one selected from the group consisting of 2-hydroxy-2-methyl-1 phenyl-1 propanone and azobisisobutyronitrile, and the lithium salt includes, but is not limited to, at least one selected from the group consisting of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate and lithium dioxalate borate.
S600: mixing oxide ceramic, a binder, lithium salt and a solvent to prepare ceramic slurry, applying the ceramic slurry on the surface of the heat-treated composite negative electrode obtained in the step S400, curing, and insulating the edge of the obtained composite negative electrode
In the step, oxide ceramic, a binder, a lithium salt and a solvent are mixed to prepare ceramic slurry, the ceramic slurry is applied to the surface of the heat-treated composite negative electrode obtained in the step S400 and then cured, and then the edge of the obtained composite negative electrode is subjected to insulation treatment. The inventor finds that the battery core lamination positive electrode is smaller than the negative electrode, and the composite negative electrode edge is subjected to insulation treatment, so that the current collector burrs at the edge of the positive electrode or the active material contacting the negative electrode can be prevented from causing short circuit. According to one embodiment of the invention, the mass ratio of the oxide ceramic to the binder to the lithium salt is (80-95): (3-5): (5-10), for example, the mass ratio is (80, 81-94, 95): (3, 3.1-4.9, 5): (5, 5.1-9.9, 10). Meanwhile, the solid content of the ceramic slurry is 40-55 wt%, for example, 40 wt%, 41 wt% … … 54 wt%, 55 wt%. The inventor finds that if the solid content of the ceramic slurry is too low, the coating leakage and the coating thickness do not reach the standard easily; and if the solid content of the ceramic slurry is too high, the problems of too thick coating thickness, coating incapability and the like are easily caused. Specifically, the insulating treatment of the composite cathode edge is performed by attaching modified silica gel to the periphery of the composite cathode, the thickness of the attached modified silica gel is not higher than the thickness of the composite anode obtained in step S300, and if the thickness of the attached modified silica gel is higher than the thickness of the composite anode, a gap is formed between the anode and the cathode, and the battery cannot work normally.
Further, the oxide ceramic includes, but is not limited to, at least one selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium tantalum oxygen, and lithium lanthanum zirconium aluminum oxygen, and the lithium salt includes, but is not limited to, at least one selected from the group consisting of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate, and lithium dioxalate borate; the solvent includes, but is not limited to, at least one selected from the group consisting of N-methylpyrrolidone, dimethylformamide, acetonitrile, ethyl acetate, and deionized water; the binder includes, but is not limited to, at least one of PVDF, PEO, and modacrylic.
S700: slicing the composite positive electrode obtained in the step S500 and the composite negative electrode obtained in the step S600, sequentially and alternately stacking to obtain a battery cell, performing heat treatment on the battery cell, welding a lug and packaging
In the step, the composite positive electrode obtained in the step S500 and the composite negative electrode obtained in the step S600 are sliced and then sequentially overlapped in a staggered manner so as to obtain a battery cell, and the battery cell is subjected to heat treatment, and then a tab is welded and packaged to obtain the solid-state battery. It should be noted that the steps of preparing the battery core by alternately stacking the composite positive electrode and the composite negative electrode, performing heat treatment on the battery core, and welding and packaging the tab are conventional operations for assembling the battery in the field, and a person skilled in the art can select the operation according to actual needs, and details are not described here.
In a second aspect of the invention, a solid-state battery is provided. According to an embodiment of the present invention, the solid-state battery is prepared by the above method. Thus, the solid-state battery has excellent safety performance and electrical performance. It should be noted that the features and advantages described above for the preparation of the solid-state battery are also applicable to the solid-state battery and will not be described herein again.
In a third aspect of the present invention, a vehicle is presented. According to an embodiment of the present invention, the vehicle has the solid-state battery described above. Therefore, the vehicle loaded with the solid-state battery with excellent safety performance and electric performance has excellent driving range. It should be noted that the features and advantages described above for the solid-state battery and the method for manufacturing the same are also applicable to the vehicle, and are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
1) Uniformly coating the lithium aluminum germanium phosphate with the particle size (D50) of 300-500nm on the surface of the ternary 622 positive electrode material by adopting an atomic layer deposition technology, wherein the coating thickness is 1-2 nm;
2) mixing the surface-modified 622 positive electrode material with lithium lanthanum zirconium tantalum oxygen, lithium bistrifluoromethanesulfonimide, modified polypropylene carbonate PPC, PVDF and SP according to a mass ratio of 90: 2: 1: 1: 2: 4 mixing the mixture with acetonitrile serving as a solvent to obtain composite anode slurry with the solid content of 55 wt%, coating the composite anode slurry on the surface of an aluminum foil current collector for three times by using a transfer coating machine to prepare a composite anode with the concentration gradient of the composite anode slurry which is sequentially reduced from the current collector to the surface of an electrode;
3) the graphite negative electrode, lithium aluminum germanium phosphate, lithium bis (trifluoromethanesulfonyl) imide, modified polyethylene oxide (PEO), polyvinylidene fluoride (PVDF) -HFP and phosphorus Sulfide (SP) are mixed according to the mass ratio: 90: 2: 1: 2: 1.5: 3.5 mixing, stirring and dispersing uniformly with a solvent DMF to obtain composite negative electrode slurry with a solid content of 45 wt%, coating the composite negative electrode slurry on the surface of a copper foil current collector by a transfer coater for three times to obtain a composite negative electrode with a composite negative electrode slurry concentration gradient which is sequentially reduced from the current collector to the surface of an electrode;
4) respectively carrying out high-temperature and high-pressure heat treatment on the obtained composite anode and composite cathode, wherein the temperature is 100 ℃, the pressure is 0.8MPa, and the time is 5 min;
5) polyethylene glycol methyl ether methacrylate, vinylene carbonate, 2-hydroxy-2-methyl-1 phenyl-1 acetone and lithium bis (trifluoromethanesulfonyl) imide are mixed according to the mass ratio of 30: 67: 0.1: 2.9, uniformly mixing, stirring and dispersing to obtain electrolyte slurry with the solid content of 40 wt%, uniformly coating the electrolyte slurry on the surface of the composite anode obtained in the step (4), and then performing ultraviolet irradiation, wherein the curing parameters are as follows: time 120min, temperature: 30 ℃;
6) lithium lanthanum zirconium tantalum oxygen, PVDF-HFP and lithium bis (trifluoromethane sulfonyl) imide are mixed according to the mass ratio of 90: 4: 6, mixing the mixture with a solvent NMP to obtain ceramic slurry with the solid content of 55 wt%, coating the ceramic slurry on the surface of the composite cathode to obtain a composite cathode, and then performing insulation treatment on the periphery of the composite cathode by adopting modified silica gel methyl phenyl silicone resin, wherein the thickness of the insulation layer is not higher than that of the composite cathode obtained in the step (3);
7) sequentially and alternately superposing the composite positive electrode obtained in the step (5) and the composite negative electrode obtained in the step (6) to prepare a battery cell, and carrying out high-temperature and high-pressure heat treatment on the battery cell at 100 ℃ and 0.7MPa for 30 min; and then welding the lugs and packaging the battery cell to obtain the solid-state battery. The solid-state battery can pass safety tests of needling, overcharging, extruding and thermal runaway, and the retention rate is 95% after 0.3C @0.3C circulation is carried out for 500 times.
Example 2
1) Uniformly coating the lithium lanthanum zirconium tantalum oxide with the particle size (D50) of 300-500nm on the surface of the ternary 523 positive electrode material by adopting an atomic layer deposition technology, wherein the coating thickness is 0.5-1 nm;
2) mixing the 523 positive electrode material subjected to surface modification with lithium lanthanum titanium oxide, lithium bistrifluoromethanesulfonimide, modified polypropylene carbonate PCC, PVDF-HFP and SP according to a mass ratio of 90: 2: 1: 1.5: 2.5: 3 mixing the mixture with a solvent NMP to obtain composite anode slurry with the solid content of 55 wt%, coating the composite anode slurry on the surface of an aluminum foil current collector for three times by using a transfer coating machine to obtain a composite anode with the concentration gradient of the composite anode slurry which is sequentially reduced from the current collector to the surface of an electrode;
3) the graphite negative electrode, lithium lanthanum zirconium tantalum oxygen, lithium bistrifluoromethanesulfonylimide, modified polyethylene oxide PEO, PVDF-HFP and SP are mixed according to the mass ratio: 90: 2: 1: 2: 1.5: 3.5 mixing, stirring and uniformly dispersing the mixture with acetonitrile serving as a solvent to obtain composite negative electrode slurry with the solid content of 45 wt%, coating the composite negative electrode slurry on the surface of a copper foil current collector for three times by using a transfer coating machine to obtain a composite negative electrode with the concentration gradient of the composite negative electrode slurry which is sequentially reduced from the current collector to the surface of the electrode;
4) respectively carrying out high-temperature and high-pressure heat treatment on the obtained composite anode and composite cathode, wherein the temperature is 90 ℃, the pressure is 0.2MPa, and the time is 15 min;
5) polyethylene glycol methyl ether methacrylate, vinylene carbonate, 2-hydroxy-2-methyl-1 phenyl-1 acetone and lithium bis (trifluoromethanesulfonyl) imide are mixed according to the mass ratio of 30: 67: 0.1: 2.9, uniformly mixing, stirring and dispersing to obtain electrolyte slurry with the solid content of 40 wt%, uniformly coating the electrolyte slurry on the surface of the composite anode obtained in the step (4), and then performing ultraviolet irradiation, wherein the curing parameters are as follows: time 100min, temperature: 35 ℃;
6) lithium lanthanum zirconium tantalum oxygen, PVDF-HFP and lithium bis (trifluoromethane sulfonyl) imide are mixed according to the mass ratio of 92: 2: 6, mixing the mixture with a solvent DMF (dimethyl formamide), coating the ceramic slurry on the surface of the composite cathode to obtain a composite cathode, and then performing insulation treatment on the peripheral edge of the composite cathode by adopting modified silica gel methyl phenyl silicone resin, wherein the thickness of the insulation layer is not higher than that of the composite cathode obtained in the step (3);
7) sequentially and alternately superposing the composite positive electrode obtained in the step (5) and the composite negative electrode obtained in the step (6) to prepare a battery cell, and carrying out high-temperature and high-pressure heat treatment on the battery cell at 90 ℃ and under 0.8MPa for 30 min; and then welding the lugs and packaging the battery cell to obtain the solid-state battery. The solid-state battery can pass the safety tests of needling, overcharging, extruding and thermal runaway, the 0.3C @0.3C cycle is carried out for 500 times, and the retention rate is 96.5%.
Example 3
1) Uniformly coating lithium lanthanum zirconium aluminum oxide with the particle size of (D50)300-500nm on the surface of the ternary 523 positive electrode material by adopting an atomic layer deposition technology, wherein the coating thickness is 3-5 nm;
2) mixing the 523 positive electrode material subjected to surface modification with aluminum oxide, lithium bis (oxalato) borate, polyether polymer PEO, PVDF-HFP and SP according to a mass ratio of 96: 1: 3: 1: 4: 5 mixing the obtained mixture with a solvent NMP to obtain composite anode slurry with the solid content of 60 wt%, coating the composite anode slurry on the surface of an aluminum foil current collector for three times by using a transfer coating machine to obtain a composite anode with the concentration gradient of the composite anode slurry which is sequentially reduced from the current collector to the surface of an electrode;
3) mixing a graphite negative electrode with titanium aluminum lithium phosphate, lithium hexafluorophosphate, polyacrylonitrile polymer PAN, PVDF-HFP and SP according to a mass ratio of 90: 6: 0.5: 4: 2.5: 8, mixing the mixture with acetonitrile serving as a solvent, stirring and dispersing uniformly to obtain composite negative electrode slurry with the solid content of 55 wt%, coating the obtained composite negative electrode slurry on the surface of a copper foil current collector for three times by using a transfer coating machine to prepare a composite negative electrode with the concentration gradient of the composite negative electrode slurry which is sequentially reduced from the current collector to the surface of an electrode;
4) respectively carrying out high-temperature and high-pressure heat treatment on the obtained composite anode and composite cathode, wherein the temperature is 80 ℃, the pressure is 0.8MPa, and the time is 5 min;
5) polyethylene glycol methyl ether methacrylate, ethylene carbonate, azodiisobutyronitrile and lithium hexafluorophosphate according to the mass ratio of 50: 45: 0.5: 10, uniformly mixing, stirring and dispersing to obtain electrolyte slurry with the solid content of 30 wt%, uniformly coating the electrolyte slurry on the surface of the composite anode obtained in the step (4), and then performing ultraviolet irradiation, wherein the curing parameters are as follows: time 90min, temperature: 40 ℃;
6) lithium lanthanum titanium oxide, PVDF-HFP and lithium bis (oxalato) borate are mixed according to the mass ratio of 95: 3: 10, mixing the mixture with a solvent DMF to obtain ceramic slurry with the solid content of 45 wt%, coating the ceramic slurry on the surface of the composite cathode to obtain a composite cathode, and then performing insulation treatment on the peripheral edge of the composite cathode by adopting modified silica gel methyl phenyl silicone resin, wherein the thickness of an insulation layer is not higher than that of the composite cathode obtained in the step (3);
7) sequentially and alternately superposing the composite positive electrode obtained in the step (5) and the composite negative electrode obtained in the step (6) to prepare a battery cell, and carrying out high-temperature and high-pressure heat treatment on the battery cell at the temperature of 80 ℃, the pressure of 0.6MPa and the time of 25 min; and then welding the lugs and packaging the battery cell to obtain the solid-state battery. The solid-state battery can pass safety tests of needling, overcharging, extruding and thermal runaway, and the retention rate is 85% after 0.3C @0.3C circulation for 500 times.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of making a solid state battery, comprising:
(1) forming a coating layer containing oxide ceramic on the surface of the positive electrode active material particles so as to obtain a surface-modified positive electrode material;
(2) mixing the surface-modified positive electrode material with oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent to prepare composite positive electrode slurry, and applying the composite positive electrode slurry on the surface of a positive electrode current collector to prepare composite positive electrodes with different concentration gradients;
(3) mixing a negative electrode material with oxide ceramic, lithium salt, polymer solid electrolyte, a binder, a conductive agent and a solvent to prepare composite negative electrode slurry, and applying the composite negative electrode slurry on the surface of a negative electrode current collector to prepare composite negative electrodes with different concentration gradients;
(4) respectively carrying out heat treatment on the composite positive electrode and the composite negative electrode;
(5) mixing a first polymer monomer, a second polymer monomer, a photoinitiator and lithium salt to prepare electrolyte slurry, applying the electrolyte slurry on the surface of the heat-treated composite positive electrode obtained in the step (4), and then curing;
(6) mixing oxide ceramic, a binder, lithium salt and a solvent to prepare ceramic slurry, applying the ceramic slurry on the surface of the heat-treated composite negative electrode obtained in the step (4), curing, and then performing insulation treatment on the edge of the obtained composite negative electrode;
(7) and (4) slicing the composite positive electrode obtained in the step (5) and the composite negative electrode obtained in the step (6), sequentially and alternately superposing to obtain a battery core, and welding a lug and packaging after heat treatment of the battery core to obtain the solid-state battery.
2. The method according to claim 1, wherein in step (1), the positive electrode active material particles are at least one selected from ternary 622 positive electrode material particles and ternary 523 positive electrode material particles;
optionally, in the step (1), the thickness of the coating layer is 0.5-10 nm.
3. The method according to claim 1 or 2, wherein in steps (1), (2), (3) and (6), the oxide ceramic is at least one selected from the group consisting of aluminum oxide, silicon dioxide, titanium dioxide, lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium lanthanum zirconium tantalum oxygen and lithium lanthanum zirconium aluminum oxygen;
optionally, in the steps (2) and (3), the polymer solid electrolyte is at least one selected from polyether polymers, polyamine polymers, polythioether polymers, polyacrylate polymers and polyacrylonitrile polymers;
optionally, in the steps (2), (3), (5) and (6), the lithium salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate and lithium dioxalate borate;
optionally, in the steps (2), (3) and (6), the solvent is at least one selected from the group consisting of N-methylpyrrolidone, dimethylformamide, acetonitrile, ethyl acetate and deionized water.
4. The method according to claim 3, wherein in the step (2), the mass ratio of the surface-modified positive electrode material to the oxide ceramic, the lithium salt, the polymer solid electrolyte, the binder and the conductive agent is (80-96): (1-8): (0.5-3): (1-4): (2-4): (3-8);
optionally, in the step (2), the solid content of the composite cathode slurry is 30-60 wt%.
5. The method according to claim 3, wherein in step (3), the mass ratio of the negative electrode material to the oxide ceramic, the lithium salt, the polymer solid electrolyte, the binder, and the conductive agent is (90-96): (0.5-6): (0.5-3): (2-4): (1.5-4): (2.5-8);
optionally, in the step (3), the solid content of the composite anode slurry is 30-55 wt%.
6. The method according to claim 3, wherein in the step (4), the heat treatment is performed at a temperature of 80 to 100 degrees Celsius and a pressure of 0.1 to 0.8MPa for a period of 5 to 15 minutes.
7. The method according to claim 3, wherein in the step (5), the mass ratio of the first polymer monomer, the second polymer monomer, the photoinitiator, and the lithium salt is (10-50): (45-80): (0.1-0.5): (1.5-10);
optionally, in the step (5), the solid content of the electrolyte slurry is 30-55 wt%;
optionally, in the step (5), the first polymer monomer is polyethylene glycol methyl ether methacrylate, the second polymer monomer is at least one selected from vinylene carbonate and ethylene carbonate, and the photoinitiator is at least one selected from 2-hydroxy-2-methyl-1 phenyl-1 acetone and azobisisobutyronitrile.
8. The method according to claim 3, wherein in the step (6), the mass ratio of the oxide ceramic, the binder and the lithium salt is (80-95): (3-5): (5-10);
optionally, in the step (6), the solid content of the ceramic slurry is 40-55 wt%.
9. A solid-state battery, characterized in that it is produced by a method according to any one of claims 1 to 8.
10. A vehicle characterized by having the solid-state battery according to claim 9.
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| CN112289995A (en) * | 2020-10-29 | 2021-01-29 | 上海电气集团股份有限公司 | Composite positive electrode slurry, positive electrode plate and solid-state battery |
| CN112786860A (en) * | 2021-01-25 | 2021-05-11 | 上海电气集团股份有限公司 | Composite positive electrode material and preparation method thereof, positive electrode slurry, positive electrode plate and all-solid-state battery |
| CN113258127A (en) * | 2021-05-31 | 2021-08-13 | 浙江大学 | Current collector-negative electrode integrated bipolar lithium secondary battery and method thereof |
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| CN113675403A (en) * | 2021-07-30 | 2021-11-19 | 华南师范大学 | Solid-state battery and preparation method and application thereof |
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| US20220376255A1 (en) * | 2021-05-24 | 2022-11-24 | Solid Energies Inc. | Silicon-Based Composite Anodes for High Energy Density, High Cycle Life Solid-State Lithium-Ion Battery |
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| US20230155168A1 (en) * | 2021-01-04 | 2023-05-18 | Bioenno Tech LLC | All Solid-State Lithium-Ion Battery Incorporating Electrolyte-Infiltrated Composite Electrodes |
| US11967678B2 (en) * | 2021-01-04 | 2024-04-23 | Solid Energies, Inc. | All solid-state lithium-ion battery incorporating electrolyte-infiltrated composite electrodes |
| CN112786860A (en) * | 2021-01-25 | 2021-05-11 | 上海电气集团股份有限公司 | Composite positive electrode material and preparation method thereof, positive electrode slurry, positive electrode plate and all-solid-state battery |
| CN112786860B (en) * | 2021-01-25 | 2021-11-16 | 上海电气集团股份有限公司 | Composite positive electrode material and preparation method thereof, positive electrode slurry, positive electrode plate and all-solid-state battery |
| CN113363414A (en) * | 2021-03-26 | 2021-09-07 | 万向一二三股份公司 | Lithium ion battery positive plate using multilayer coated ternary positive material and preparation method thereof |
| US20220376255A1 (en) * | 2021-05-24 | 2022-11-24 | Solid Energies Inc. | Silicon-Based Composite Anodes for High Energy Density, High Cycle Life Solid-State Lithium-Ion Battery |
| US11888162B2 (en) * | 2021-05-24 | 2024-01-30 | Solid Energies Inc. | Silicon-based composite anodes for high energy density, high cycle life solid-state lithium-ion battery |
| CN113258127A (en) * | 2021-05-31 | 2021-08-13 | 浙江大学 | Current collector-negative electrode integrated bipolar lithium secondary battery and method thereof |
| CN113258127B (en) * | 2021-05-31 | 2023-09-15 | 浙江大学 | Current collector-negative electrode integrated bipolar lithium secondary battery and method thereof |
| CN113675403A (en) * | 2021-07-30 | 2021-11-19 | 华南师范大学 | Solid-state battery and preparation method and application thereof |
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