CN112652815A - Low-internal-resistance all-solid-state battery and preparation method thereof - Google Patents
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Abstract
The invention provides a low-internal-resistance all-solid-state battery and a preparation method thereof. The invention adopts hard carbon and conductive polymer as buffer layers, which inhibits the expansion problem of pole pieces in the charge and discharge processes of the negative electrode, ensures that the negative electrode is in good contact with the interface of the solid electrolyte, improves the interface stability between the solid electrolyte and the negative electrode, and reduces the internal resistance of the interface.
Description
Technical Field
The invention relates to the field of batteries, in particular to an all-solid-state battery with low internal resistance and a preparation method thereof.
Background
The traditional lithium ion battery adopts liquid organic electrolyte as electrolyte, and has larger potential safety hazard when storing electric quantity in large capacity, so that the development of the all-solid-state lithium battery is the first choice for fundamentally solving the safety problem of the lithium ion battery. A general all-solid-state lithium battery is composed of positive and negative electrodes and a solid electrolyte between the positive and negative electrodes. The solid electrolyte is used as a component of the core of the solid battery, wherein the room-temperature ionic conductivity of the sulfide solid electrolyte is high, but the preparation process has strict requirements on the environment; the oxide solid electrolyte has good mechanical property and high ionic conductivity, but has poor processing property, and is difficult to realize the mass production of large-capacity solid batteries; the polymer solid electrolyte has good processability, but low room temperature ionic conductivity.
At present, the problems of low conductivity, large interface internal resistance between the solid electrolyte and an electrode material and the like generally exist in the solid electrolyte. The solid-solid interface problem exists between the electrolyte and the electrode of the all-solid-state lithium battery, and comprises the problems of large interface resistance, poor interface stability, interface stress change and the like. At present, the research ideas aiming at the problems mainly comprise doping modification on a solid electrolyte to improve the ionic conductivity, surface modification treatment on an electrode material, nanocrystallization of the electrode material, development of a novel or optimized existing electrode material to reduce the volume effect and the like.
Disclosure of Invention
The invention provides an all-solid-state battery with low internal resistance and a preparation method thereof, and solves the problem of high internal resistance of the all-solid-state battery. The positive electrode layer and the solid electrolyte layer are integrally prepared, and the number of interfaces is reduced, so that the influence of interface impedance on the solid battery is reduced. The surface of the negative electrode layer is coated with a layer of porous hard carbon and conductive polymer to serve as a buffer layer to buffer the volume effect of the negative electrode in the charging and discharging processes, the interface stability between the solid electrolyte layer and the negative electrode layer is improved, meanwhile, the buffer layer has high lithium storage capacity and electronic conductivity, and meanwhile, the negative electrode with the surface coated with the buffer layer is soaked in lithium salt solution to improve the ionic conductivity, so that the rate capability and the cycle performance of the battery are further improved.
The technical scheme for realizing the invention is as follows:
the low-internal-resistance all-solid-state battery comprises a positive electrode layer and a composite negative electrode layer, wherein a solid electrolyte layer is arranged between the positive electrode layer and the composite negative electrode layer, the solid electrolyte layer and the positive electrode layer are integrally prepared by solidification, the composite negative electrode layer comprises a negative electrode layer and a buffer layer, the buffer layer is composed of hard carbon and conductive polymers, and the buffer layer and the negative electrode layer are integrally prepared.
And the composite negative electrode layer is dried after being soaked in a lithium salt solution.
The solid electrolyte layer adopts a polymer solid electrolyte, the polymer solid electrolyte comprises a polymer matrix and lithium salt, and the polymer matrix is one or a mixture of polyethylene oxide, polysiloxane, polyethylene terephthalate, polyvinylidene fluoride, polyethylene carbonate, polypropylene carbonate or polymethyl methacrylate.
The lithium salt comprises LiPF6、LiTFSI、LiClO4、LiBO4、LiAsF6、LiCF3SO3Or LiBC4O8One or more of them are mixed.
The hard carbon particles D50Is 7-12 mu m, and the specific surface area is 600-1200m2Between/g, the volume of the macropores accounts for 60-80% of the volume of the pores; the conductive polymer comprises one or more of polyethylene dioxythiophene, polyacetylene, polythiophene, polypyrrole or polyaniline.
The preparation method of the all-solid-state battery with low internal resistance comprises the following steps:
(1) adding a positive active substance, a conductive agent and a binder into a solvent, adopting a wet homogenization process, adding the positive active substance material in two batches, stirring at a high speed in vacuum to obtain slurry, wherein the solid content of the slurry is 65-75%, the viscosity of the slurry is 6000-12000 mPa.s, and coating the positive slurry on an aluminum foil by adopting a coating machine in an intermittent coating mode to obtain a positive plate;
(2) dissolving a polymer solid electrolyte in acetonitrile serving as a solvent, adding a plasticizer and a filler after stirring, stirring into transparent liquid under the vacuum degree of-0.1 MPa, coating slurry on a positive electrode sheet by adopting a coating machine in an intermittent coating mode, wherein the coating thickness is 30-50 mu m, and drying the slurry by using a 100 ℃ oven to be integrated with the positive electrode layer in a curing manner to obtain a positive electrode layer;
(3) adding a negative electrode active substance, superconducting carbon black and a binder sodium carboxymethylcellulose (CMC) into a hydrosolvent, adding the negative electrode active substance material in two batches by adopting a wet-process homogenate process, and stirring at a high speed in vacuum to obtain negative electrode slurry; coating the negative electrode slurry on a copper foil in an intermittent coating mode by adopting a coating machine to obtain a negative electrode sheet;
(4) dissolving hard carbon and a conductive polymer in a CMC (carboxy methyl cellulose) glue solution, stirring, coating slurry on a negative electrode plate in an intermittent coating mode by using a coating machine, wherein the coating thickness is 20-30 mu m, and drying by using a 60 ℃ oven to integrate with the negative electrode layer in a curing manner to obtain a composite negative electrode layer;
(5) soaking the composite negative electrode layer in a lithium salt solution for 1-5min, and drying by an oven;
(6) and according to the fact that the surface capacity of the negative electrode is 1.0-1.2 times of the surface capacity of the positive electrode, the size of the negative electrode is 0-2 mm larger than that of the positive electrode, and the positive electrode and the negative electrode are subjected to the working procedures of rolling, die cutting, laminating, cold hot pressing, tab welding, packaging, baking, liquid injection, formation, capacity grading and the like, and the electric core is manufactured.
The percentage content of each substance in the step (1) is as follows: 96-98% of positive electrode active material, 1-2% of conductive agent and 1-2% of binder; the positive active substance comprises one or a mixture of more of ternary materials of nickel cobalt lithium manganate, nickel cobalt lithium aluminate (NCM, NCA), Lithium Cobaltate (LCO), lithium iron phosphate (LFE) and high-voltage Lithium Manganate (LMO); the conductive agent is one or more of acetylene black, superconducting carbon black, conductive graphite, carbon nano tubes, carbon fibers, vapor grown fibers or graphene; the binder is one or more of polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber, organic olefine acid, carboxylic acid esters or sodium alginate.
The coating surface density of the anode slurry in the step (2) is 8-25 mg/cm2。
In the step (3), the percentage content of each substance is 94-98% of negative active substance, 1-3% of conductive agent and 1-3% of binder, and the negative active substance is one or a mixture of more of silicon carbon, silicon oxygen carbon and graphite; in the step (3), the solid content of the slurry is 35-55%, the viscosity of the slurry is 4000-8000 mPa.s, and the coating surface density is 5-15 mg/cm2。
In the step (4), the mass percent of the hard carbon is 47-53%, and the mass percent of the conductive polymer is 47-53%.
The invention has the beneficial effects that:
(1) the invention adopts hard carbon and conductive polymer as buffer layers, which inhibits the expansion problem of pole pieces in the charge and discharge processes of the negative electrode, ensures that the negative electrode is in good contact with the interface of the solid electrolyte, improves the interface stability between the solid electrolyte and the negative electrode, and reduces the internal resistance of the interface.
(2) The hard carbon and the conductive polymer have good electronic conductivity, and after being soaked by lithium salt, the hard carbon and the conductive polymer have higher ion transmission capability, can further reduce the internal resistance of the battery, and improve the rate capability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a diagram of a soft pack full cell cycle of example 1.
Fig. 2 is a pouch full cell cycle diagram of example 2.
Fig. 3 is a diagram of a comparative example soft pack full cell cycle.
Fig. 4 is a schematic structural view of a battery.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The positive electrode layer, the solid electrolyte layer, the negative electrode layer and the all-solid-state battery of this example were prepared by the following steps:
(1) integrally preparing the positive electrode layer and the solid layer: adding a positive active material nickel cobalt lithium manganate (NCM 811), superconducting carbon black and polyvinylidene fluoride into a double-planet stirrer with a proper amount of NMP solvent according to a mass ratio of 97:1:2, adopting a wet-process homogenization process, adding the positive active material in two batches, and stirring at a high speed in vacuum, wherein the solid content of the slurry is 70%, and the viscosity of the slurry is 8000 mPa.s. Coating the positive electrode slurry on an aluminum foil by a coater in an intermittent coating mode, wherein the coating surface density is 12.5mg/cm2。
(2) Mixing polymer polyethylene oxide and lithium salt LiPF6Dissolving in organic solvent acetonitrile, adding a plasticizer and a filler after stirring and dissolving, stirring into transparent liquid under the vacuum degree of-0.1 MPa, coating slurry on the positive plate by adopting a coating machine in an intermittent coating mode, wherein the coating thickness is 30 mu m, and drying by an oven at 100 ℃ to be integrated with the curing of the positive plate layer.
(3) Preparing a negative electrode layer: adding a negative active substance silicon carbon (SiC 500), superconducting carbon black and sodium carboxymethylcellulose into a double-planet stirrer with a proper amount of hydrosolvent according to a mass ratio of 96:2:2, adopting a wet homogenization process, adding the negative active substance material in two batches, and stirring at a high speed in vacuum, wherein the solid content of the slurry is 45%, and the viscosity of the slurry is 5000 mPa.s. Coating the negative electrode slurry on a copper foil by adopting a coating machine in an intermittent coating mode, wherein the coating surface density is 5mg/cm2。
(4) Using hard carbon particles D50Is 10 mu m, and the specific surface area is 900m2/g，The volume of the macropores accounts for 75% of the volume of the pores, the conductive polymer is polyaniline, the weight percentage of the hard carbon is 47%, the mass percentage of the polyaniline is 53%, the conductive polymer and the hard carbon are dissolved in CMC glue solution and stirred, slurry is coated on the negative electrode piece in an intermittent coating mode by a coating machine, the coating thickness is 20 mu m, and the negative electrode layer is dried by a 60 ℃ oven and solidified into a whole.
(5) And soaking the prepared composite negative electrode layer in a lithium salt LiTFSI solution for 1min, and drying in an oven.
(6) Preparing an all-solid-state battery: the negative plate surface capacity of the all-solid-state battery is 1.1 times of the positive plate surface capacity, and the size of the negative plate is 1mm larger than that of the positive plate. And the positive and negative pole pieces are subjected to processes of rolling, die cutting, laminating, cold and hot pressing, tab welding, packaging, baking, liquid injection, formation, capacity grading and the like to complete the manufacture of the battery cell.
Example 2
The positive electrode layer, the solid electrolyte layer, the negative electrode layer and the all-solid-state battery of this example were prepared by the following steps:
(1) integrally preparing the positive electrode layer and the solid layer: adding a positive active material Lithium Cobaltate (LCO), superconducting carbon black and polyvinylidene fluoride into a double-planet stirrer with a proper amount of NMP solvent according to a mass ratio of 98:1:1, adopting a wet-process homogenization process, adding the positive active material in two batches, and stirring at a high speed in vacuum until the solid content of the slurry is 68% and the viscosity of the slurry is 7000mPa. Coating the positive electrode slurry on an aluminum foil by a coater in an intermittent coating mode, wherein the coating surface density is 20mg/cm2。
(2) Dissolving polymer polyvinylidene fluoride and lithium salt LiTFSI in organic solvent acetonitrile, adding plasticizer and filler after stirring and dissolving, stirring into transparent liquid under the vacuum degree of-0.1 MPa, coating slurry on an anode sheet by a coating machine in an intermittent coating mode, wherein the coating thickness is 40 mu m, and drying the anode sheet by a 100 ℃ oven to be integrated with the anode layer in a curing mode.
(3) Preparing a negative electrode layer: adding a negative active material silicon oxygen carbon (SiOC 450), superconducting carbon black and sodium hydroxymethyl cellulose into a double-planet stirrer with a proper amount of hydrosolvent according to a mass ratio of 97:1:2, and adopting wet methodThe method adopts a homogenizing process, wherein the negative active material is added in two batches, and the mixture is stirred at a high speed in vacuum, wherein the solid content of the slurry is 46 percent, and the viscosity of the slurry is 6000 mPa.s. Coating the negative electrode slurry on an aluminum foil by adopting a coating machine in an intermittent coating mode, wherein the coating surface density is 8mg/cm2。
(4) Using hard carbon particles D50Is 12 mu m and the specific surface area is 100m2The conductive polymer is polyethylene dioxythiophene, the weight percentage of hard carbon is 50%, the mass percentage of polyethylene dioxythiophene is 50%, the two are dissolved in CMC glue solution and stirred, slurry is coated on a negative electrode piece in an intermittent coating mode by a coating machine, the coating thickness is 30 mu m, and the negative electrode piece is dried by a 60 ℃ oven and is solidified into a whole.
(5) And soaking the prepared composite negative electrode layer in a lithium salt LiTFSI solution for 3min, and drying in an oven.
(6) Preparing an all-solid-state battery: the negative plate surface capacity of the all-solid-state battery is 1.05 times of the positive plate surface capacity, and the size of the negative plate is 1mm larger than that of the positive plate. And the positive and negative pole pieces are subjected to processes of rolling, die cutting, laminating, cold and hot pressing, tab welding, packaging, baking, liquid injection, formation, capacity grading and the like to complete the manufacture of the battery cell.
Example 3
The positive electrode layer, the solid electrolyte layer, the negative electrode layer and the all-solid-state battery of this example were prepared by the following steps:
(1) integrally preparing the positive electrode layer and the solid layer: adding a positive active material lithium iron phosphate (LFP), superconducting carbon black and polyvinylidene fluoride into a double-planet stirrer with a proper amount of NMP solvent according to a mass ratio of 98:1:1, adopting a wet-process homogenization process, adding the positive active material in two batches, and stirring at a high speed in vacuum, wherein the solid content of the slurry is 69%, and the viscosity of the slurry is 9000 mPa.s. Coating the positive electrode slurry on an aluminum foil by a coater in an intermittent coating mode, wherein the coating surface density is 18mg/cm2。
(2) Mixing polymer of polyethylene carbonate and lithium salt LiPF6Dissolving in organic solvent acetonitrile, stirring for dissolving, adding plasticizer and filler, and stirring under-0.1 MPa vacuum degreeStirring into transparent liquid, coating the slurry on the positive electrode plate by a coating machine in an intermittent coating mode, wherein the coating thickness is 50 mu m, and drying by an oven at 100 ℃ to be integrated with the positive electrode layer in a curing mode.
(3) Preparing a negative electrode layer: adding a negative active substance silicon oxygen carbon (SiOC 450), superconducting carbon black and sodium hydroxymethyl cellulose into a double-planet stirrer with a proper amount of hydrosolvent according to a mass ratio of 97:1:2, adopting a wet homogenization process, adding the negative active substance material in two batches, stirring at a high speed in vacuum, wherein the solid content of the slurry is 45%, and the viscosity of the slurry is 6500 mPa.s. Coating the negative electrode slurry on an aluminum foil by adopting a coating machine in an intermittent coating mode, wherein the coating surface density is 8mg/cm2。
(4) Using hard carbon particles D50Is 7 mu m, and the specific surface area is 900m2The conductive polymer is polyacetylene, the weight percentage of the hard carbon is 53%, the mass percentage of the polyacetylene is 47%, the polyacetylene and the hard carbon are dissolved in CMC glue solution and stirred, the slurry is coated on a negative electrode sheet by a coating machine in an intermittent coating mode, the coating thickness is 30 mu m, and the negative electrode sheet is dried by a 60 ℃ oven and is solidified into a whole.
(5) And soaking the prepared composite negative electrode layer in a lithium salt LiTFSI solution for 5min, and drying in an oven.
(6) Preparing an all-solid-state battery: the negative plate surface capacity of the all-solid-state battery is 1.05 times of the positive plate surface capacity, and the size of the negative plate is 1mm larger than that of the positive plate. And the positive and negative pole pieces are subjected to processes of rolling, die cutting, laminating, cold and hot pressing, tab welding, packaging, baking, liquid injection, formation, capacity grading and the like to complete the manufacture of the battery cell.
Example 4
The positive electrode layer, the solid electrolyte layer, the negative electrode layer and the all-solid-state battery of this example were prepared by the following steps:
(1) integrally preparing the positive electrode layer and the solid layer: adding lithium iron lithium phosphate (LMO) as a positive active material, superconducting carbon black and polyvinylidene fluoride into a double-planet stirrer with a proper amount of NMP solvent according to a mass ratio of 98:1:1, adopting a wet-process homogenization process, adding the positive active material in two batches,stirring at high speed in vacuum to ensure that the solid content of the slurry is 72 percent and the viscosity of the slurry is 7500 mPa.s. Coating the positive electrode slurry on an aluminum foil by using a coater in an intermittent coating mode, wherein the coating surface density is 13mg/cm2。
(2) Mixing polymer of polyethylene carbonate and lithium salt LiPF6Dissolving in organic solvent acetonitrile, adding a plasticizer and a filler after stirring and dissolving, stirring into transparent liquid under the vacuum degree of-0.1 MPa, coating slurry on an anode piece by adopting a coating machine in an intermittent coating mode, wherein the coating thickness is 50 mu m, and drying by an oven at 100 ℃ to be integrated with the anode layer curing.
(3) Preparing a negative electrode layer: adding a negative active substance silicon oxygen carbon (SiOC 450), superconducting carbon black and sodium hydroxymethyl cellulose into a double-planet stirrer with a proper amount of hydrosolvent according to a mass ratio of 97:1:2, adopting a wet homogenization process, adding the negative active substance material in two batches, stirring at a high speed in vacuum, wherein the solid content of the slurry is 45%, and the viscosity of the slurry is 6500 mPa.s. Coating the negative electrode slurry on an aluminum foil by adopting a coating machine in an intermittent coating mode, wherein the coating surface density is 8.5mg/cm2。
(4) Using hard carbon particles D50Is 8 mu m, and the specific surface area is 900m2And/g, the volume of the large pores is 80% of the volume of the pores, the conductive polymer is polythiophene, the weight percentage of the hard carbon is 48%, the mass percentage of the polythiophene is 52%, the conductive polymer and the hard carbon are dissolved in CMC glue solution and stirred, the slurry is coated on the negative electrode piece in an intermittent coating mode by a coating machine, the coating thickness is 30 mu m, and the slurry is dried by a 60 ℃ oven and is solidified into a whole with the negative electrode layer.
(5) And soaking the prepared composite negative electrode layer in a lithium salt LiTFSI solution for 4min, and drying in an oven.
(6) Preparing an all-solid-state battery: the negative pole piece surface capacity in the all-solid-state battery is 1.05 times of the positive pole piece surface capacity, and the size of the negative pole piece is 0.8mm larger than that of the positive pole piece. And the positive and negative pole pieces are subjected to processes of rolling, die cutting, laminating, cold and hot pressing, tab welding, packaging, baking, liquid injection, formation, capacity grading and the like to complete the manufacture of the battery cell.
Comparative example
This comparative example was prepared from a positive electrode layer, a solid electrolyte layer, a negative electrode layer, and an all-solid battery by the following steps:
(1) integrally preparing the positive electrode layer and the solid layer: adding a positive active material Lithium Cobaltate (LCO), superconducting carbon black and polyvinylidene fluoride into a double-planet stirrer with a proper amount of NMP solvent according to a mass ratio of 98:1:1, adopting a wet-process homogenization process, adding the positive active material in two batches, and stirring at a high speed in vacuum until the solid content of the slurry is 68% and the viscosity of the slurry is 7000mPa. Coating the positive electrode slurry on an aluminum foil by a coater in an intermittent coating mode, wherein the coating surface density is 20mg/cm2。
(2) Dissolving polymer polyvinylidene fluoride and lithium salt LiTFSI in organic solvent acetonitrile, adding plasticizer and filler after stirring and dissolving, stirring into transparent liquid under the vacuum degree of-0.1 MPa, coating slurry on an anode sheet by a coating machine in an intermittent coating mode, wherein the coating thickness is 40 mu m, and drying the anode sheet by a 100 ℃ oven to be integrated with the anode layer in a curing mode.
(3) Preparing a negative electrode layer: adding a negative active material silicon oxygen carbon (SiOC 450), superconducting carbon black and sodium hydroxymethyl cellulose into a double-planet stirrer with a proper amount of hydrosolvent according to a mass ratio of 97:1:2, adopting a wet homogenization process, adding the negative active material in two batches, and stirring at a high speed in vacuum, wherein the solid content of the slurry is 46%, and the viscosity of the slurry is 6000mPa. Coating the negative electrode slurry on an aluminum foil by adopting a coating machine in an intermittent coating mode, wherein the coating surface density is 8mg/cm2。
(4) Preparing an all-solid-state battery: the negative plate surface capacity of the all-solid-state battery is 1.05 times of the positive plate surface capacity, and the size of the negative plate is 1mm larger than that of the positive plate. And the positive and negative pole pieces are subjected to processes of rolling, die cutting, laminating, cold and hot pressing, tab welding, packaging, baking, liquid injection, formation, capacity grading and the like to complete the manufacture of the battery cell.
Table 1: data for all solid state pouch full cells of examples 1-4 and comparative examples
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An all-solid-state battery with low internal resistance, comprising a positive electrode layer and a composite negative electrode layer, characterized in that: the solid electrolyte layer is arranged between the positive electrode layer and the composite negative electrode layer, the solid electrolyte layer and the positive electrode layer are integrally prepared by solidification, the composite negative electrode layer comprises a negative electrode layer and a buffer layer, the buffer layer is composed of hard carbon and conductive polymers, and the buffer layer and the negative electrode layer are integrally prepared.
2. The all-solid-state battery with low internal resistance according to claim 1, characterized in that: and the composite negative electrode layer is dried after being soaked in a lithium salt solution.
3. The all-solid-state battery with low internal resistance according to claim 1, characterized in that: the solid electrolyte layer adopts polymer solid electrolyte, the polymer solid electrolyte comprises a polymer matrix and lithium salt, and the polymer matrix is one or a mixture of polyethylene oxide, polysiloxane, polyethylene terephthalate, polyvinylidene fluoride, polyethylene carbonate, polypropylene carbonate or polymethyl methacrylate.
4. The all-solid-state battery with low internal resistance according to claim 2, characterized in that: the lithium salt comprises LiPF6、LiTFSI、LiClO4、LiBO4、LiAsF6、LiCF3SO3Or LiBC4O8One or more of them are mixed.
5. The all-solid-state battery with low internal resistance according to claim 1, characterized in that: hard carbon particles D50Is 7-12 mu m, and the specific surface area is 600-1200m2Between/g, the volume of the macropores accounts for 60-80% of the volume of the pores; the conductive polymer comprises polyethylene dioxythiaOne or more of thiophene, polyacetylene, polythiophene, polypyrrole or polyaniline.
6. The method for producing an all-solid-state battery with low internal resistance according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) adding a positive active substance, a conductive agent and a binder into a solvent, adopting a wet homogenization process, adding the positive active substance material in two batches, stirring at a high speed in vacuum to obtain slurry, wherein the solid content of the slurry is 65-75%, the viscosity of the slurry is 6000-12000 mPa.s, and coating the positive slurry on an aluminum foil by adopting a coating machine in an intermittent coating mode to obtain a positive plate;
(2) dissolving a polymer solid electrolyte in a solvent, adding a plasticizer and a filler after stirring, stirring into a transparent liquid under the vacuum degree of-0.1 MPa, coating slurry on an anode sheet by adopting a coating machine in an intermittent coating mode, wherein the coating thickness is 30-50 mu m, and drying by using a 100 ℃ oven to be integrated with the anode layer in a curing manner to obtain a solid electrolyte layer;
(3) adding a negative electrode active substance, superconducting carbon black and sodium carboxymethylcellulose into a hydrosolvent, adding the negative electrode active substance material in two batches by adopting a wet-process homogenate process, and stirring at a high speed in vacuum to obtain negative electrode slurry; coating the negative electrode slurry on a copper foil in an intermittent coating mode by adopting a coating machine to obtain a negative electrode sheet;
(4) dissolving hard carbon and a conductive polymer in a CMC (carboxy methyl cellulose) glue solution, stirring, coating slurry on a negative electrode plate in an intermittent coating mode by using a coating machine, wherein the coating thickness is 20-30 mu m, and drying by using a 60 ℃ oven to integrate with the negative electrode layer in a curing manner to obtain a composite negative electrode layer;
(5) soaking the composite negative electrode layer in a lithium salt solution for 1-5min, and drying by an oven;
(6) and preparing the battery according to the conditions that the surface capacity of the negative electrode is 1.0-1.2 times of the surface capacity of the positive electrode, and the size of the negative electrode is 0-2 mm larger than that of the positive electrode.
7. The method of claim 6, wherein: the percentage content of each substance in the step (1) is as follows: 96-98% of positive electrode active material, 1-2% of conductive agent and 1-2% of binder; the conductive agent is one or more of acetylene black, superconducting carbon black, conductive graphite, carbon nano tubes, carbon fibers, vapor grown fibers or graphene; the binder is one or more of polyvinylidene fluoride, sodium carboxymethylcellulose, styrene butadiene rubber, organic olefine acid, carboxylic acid esters or sodium alginate.
8. The method of claim 6, wherein: the coating surface density of the anode slurry in the step (2) is 8-25 mg/cm2。
9. The method of claim 6, wherein: the percentage content of each substance in the step (3) is 94-98% of negative active substance, 1-3% of conductive agent and 1-3% of binder; in the step (3), the solid content of the slurry is 35-55%, the viscosity of the slurry is 4000-8000 mPa.s, and the coating surface density is 5-15 mg/cm2。
10. The method of claim 6, wherein: in the step (4), the mass percent of the hard carbon is 47-53%, and the mass percent of the conductive polymer is 47-53%.
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