CN116825947A - Positive electrode plate of solid-state battery and preparation method thereof - Google Patents

Positive electrode plate of solid-state battery and preparation method thereof Download PDF

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Publication number
CN116825947A
CN116825947A CN202310805619.9A CN202310805619A CN116825947A CN 116825947 A CN116825947 A CN 116825947A CN 202310805619 A CN202310805619 A CN 202310805619A CN 116825947 A CN116825947 A CN 116825947A
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positive electrode
current collector
solid
lithium
state battery
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陈少杰
郑传佐
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Svolt Energy Technology Wuxi Co Ltd
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Svolt Energy Technology Wuxi Co Ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Abstract

The application provides a solid-state battery positive plate and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Mixing an anode active material, a conductive agent, a binder and a solvent to obtain slurry, and coating the slurry on the surface of a porous current collector to obtain the porous current collector coated with the active material; (2) Mixing a polymer precursor, an initiator and lithium salt to obtain a mixed material solution, arranging the mixed material solution on the surface and/or inside of a porous current collector coated with an active substance, and carrying out in-situ polymerization reaction to obtain the solid-state battery positive electrode plate. Can solve the problems of side reaction between the solid electrolyte and the positive electrode material and poor multiplying power and circulation caused by high interface impedance.

Description

Positive electrode plate of solid-state battery and preparation method thereof
Technical Field
The application belongs to the technical field of solid-state batteries, and relates to a solid-state battery positive electrode plate and a preparation method thereof.
Background
With the great development of new energy automobiles, the current liquid batteries using liquid electrolyte cannot meet the pursuit of higher energy density and safer lithium ion batteries. The development of all-solid-state batteries using solid-state electrolytes instead of liquid electrolytes is the most effective means to meet the higher demands of people for ion batteries.
The high-nickel ternary material has higher theoretical capacity, better safety performance and excellent cycle stability, and gradually becomes a positive electrode material widely applied in lithium ion batteries.
CN113394383a discloses a coating method of a positive electrode material for a sulfide solid state battery. The method comprises the following steps: (1) Placing a positive electrode material in a reaction chamber of an ALD apparatus; (2) When the temperature of the reaction chamber reaches a first set value, loading all precursor sources into the reaction chamber through inert gas, and depositing a layer of fast ion conductor on the surface of the positive electrode material; (3) Replacing a precursor source, and continuously loading a sulfide electrolyte precursor source to the reaction chamber through inert gas when the temperature of the reaction chamber reaches a second set value, so as to deposit a layer of sulfide solid electrolyte on the surface of the fast ion conductor layer; (4) And directly annealing the coated positive electrode material in an ALD reaction chamber, and naturally cooling to obtain the double-layer coated positive electrode material.
CN115863612a discloses a positive electrode material, a preparation method and application thereof, comprising the following steps: A. dissolving zinc salt in a solvent to obtain zinc salt solution; B. dissolving 2-methylimidazole in the solution, and adding a cobalt-containing positive electrode to obtain a suspension; C. adding a nucleating agent and a surfactant into the suspension, adding a zinc salt solution into the mixed solution, stirring, heating, separating and drying to obtain a positive electrode material with a coating layer; D. and (3) calcining the positive electrode material in an oxygen-containing atmosphere.
According to the scheme, the positive electrode material is directly coated, ALD coating can uniformly coat the whole positive electrode particles, but the ALD coated material is usually a fast ion conductor with weaker conductive capability, ALD coating cost is very high, wet coating is usually required to have a harsher environment, and a process is complex, on the other hand, the interface impedance of the prepared positive electrode material is higher, and after long circulation, the capacity retention rate is lower.
Disclosure of Invention
The application aims to provide a solid-state battery positive electrode plate and a preparation method thereof. Can solve the problems of side reaction between the solid electrolyte and the positive electrode material and poor multiplying power and circulation caused by high interface impedance.
In order to achieve the aim of the application, the application adopts the following technical scheme:
in a first aspect, the present application provides a method for preparing a positive electrode sheet of a solid-state battery, the method comprising the steps of:
(1) Mixing an anode active material, a conductive agent, a binder and a solvent to obtain slurry, and coating the slurry on the surface of a porous current collector to obtain the porous current collector coated with the active material;
(2) And mixing the polymer precursor, the initiator and the lithium salt to obtain a mixed material solution, arranging the mixed material solution on the surface and/or inside of the porous current collector coated with the active material, and carrying out in-situ polymerization reaction to obtain the solid-state battery anode plate.
The porous current collector with large specific surface area is used, so that the positive electrode material can be uniformly dispersed on the current collector, and the subsequent coating of the positive electrode material is facilitated. And a polymer layer is coated on the surface of the positive electrode material in situ by using a solution in-situ polymerization mode, so that the direct contact between the positive electrode material and the solid electrolyte layer is effectively isolated, and the electrochemical performance of the positive electrode material in the solid battery is obviously improved.
Preferably, the positive electrode active material of step (1) includes any one or a combination of at least two of lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium cobalt oxide, and lithium manganese oxide.
Preferably, the conductive agent includes any one or a combination of at least two of acetylene black, ketjen black, conductive carbon black, carbon nanotubes, or graphene.
Preferably, the binder comprises any one or a combination of at least two of polyvinylidene fluoride, guar gum, sodium alginate or carboxymethyl cellulose.
Preferably, the solvent comprises any one or a combination of at least two of N-methylpyrrolidone, N-dimethylacetamide, acetonitrile or xylene.
Preferably, the porous current collector of step (1) comprises porous aluminum foam.
Preferably, the thickness of the porous current collector is 0.3 to 0.8mm, for example: 0.3mm, 0.4mm, 0.5mm, 0.6mm or 0.8mm, etc.
Preferably, the porous current collector of step (1) is pretreated before coating.
Preferably, the pretreatment comprises immersing the porous current collector in concentrated nitric acid, reacting for 10 hours at 120 ℃, cooling, washing with absolute ethanol, and drying.
Preferably, the polymer precursor of step (2) comprises any one or a combination of at least two of ethylene glycol dimethyl ether, ethylene glycol methyl ether acrylate, 1, 3-dioxolane, ethylene glycol diacrylate or triethylene glycol dimethacrylate.
Preferably, the initiator comprises benzoyl peroxide and/or azobisisobutyronitrile.
Preferably, the lithium salt comprises any one or a combination of at least two of lithium bis (fluoromethylsulfonimide), lithium bis (trifluoromethylsulfonimide), lithium hexafluoroborate, lithium hexafluorophosphate or lithium perchlorate.
Preferably, the mass ratio of the polymer precursor and the positive electrode active material in step (2) is (0.5 to 3): 1, for example: 0.5:1, 1:1, 1.5:1, 2:1, or 3:1, etc.
Preferably, the mass ratio of the polymer precursor and the initiator in step (2) is 1 (0.001 to 0.005), for example: 1:0.001, 1:0.002, 1:0.003, 1:0.004, or 1:0.005, etc.
Preferably, the lithium salt (1 to 1.5) of step (2) is 3, for example: 1:3, 1.1:3, 1.2:3, 1.4:3, or 1.5:3, etc.
Preferably, the arrangement of step (2) comprises dropping and/or injecting the mixture solution into the active material coated porous current collector or directly immersing the active material coated porous current collector into the mixture solution.
Preferably, the in situ polymerization reaction is carried out at a temperature of 60 to 80 ℃, for example: 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃ and the like.
Preferably, the in situ polymerization is carried out for a period of time ranging from 5 to 30 hours, for example: 5h, 10h, 15h, 20h or 30h, etc.
In a second aspect, the present application provides a solid state battery positive electrode sheet produced by the method as described in the first aspect.
In a third aspect, the present application provides an all-solid-state battery comprising a solid-state battery positive electrode tab as described in the second aspect.
Compared with the prior art, the application has the following beneficial effects:
(1) The application obtains the solid-state battery anode plate through in-situ polymerization coating, and the porous current collector with high specific surface area is used to uniformly distribute anode particles. Can solve the problems of side reaction between the solid electrolyte and the positive electrode material and poor multiplying power and circulation caused by high interface impedance.
(2) The first-turn discharge specific capacity of the solid-state battery positive electrode plate manufactured by the method can reach more than 199.8mAh/g under 0.1C, the capacity retention rate can reach more than 99.5% after 100 weeks, and the capacity retention rate can reach more than 92% after 500 weeks.
Drawings
Fig. 1 is an SEM image of a positive electrode sheet of a solid-state battery according to example 1 of the present application.
Fig. 2 is an SEM enlarged view of the positive electrode tab of the solid-state battery according to example 1 of the present application.
Detailed Description
The technical scheme of the application is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the application and are not to be construed as a specific limitation thereof.
The porous current collectors of the examples and comparative examples of the present application were pretreated by the following method:
cutting porous aluminum foam into proper size, placing the proper size into a reaction kettle, adding concentrated nitric acid into the reaction kettle without excessive porous aluminum foam, then placing the reaction kettle into a vacuum oven for reaction for 10 hours at 120 ℃, taking out the porous aluminum foam after complete cooling, immediately completely washing the concentrated nitric acid with absolute ethyl alcohol, and drying the washed porous aluminum foil for later use.
Example 1
The embodiment provides a solid-state battery positive electrode plate, which is prepared by the following steps:
(1) 9g of LiNi is weighed 0.8 Mn 0.1 Co 0.1 O 2 (NMC 811), 1g of conductive carbon black super P and 1g of PVDF, adding the materials into NMP solution, uniformly stirring at a rotation speed of 400rpm to obtain homogeneous slurry, putting the slurry into a vacuum deaerator for deaeration treatment, then coating the slurry with bubbles removed on a porous foam aluminum current collector by using a scraper, and drying the porous foam aluminum current collector in a vacuum drying oven at 90 ℃ for 12 hours to obtain the porous current collector coated with active substances;
(2) In a glove box (O) 2 ≤0.01ppm、H 2 O is less than or equal to 0.01 ppm), 6g of ethylene glycol dimethyl ether is measured, 2g of lithium bistrifluoromethylsulfonyl imide (LiTFSI) and 0.006g of Azodiisobutyronitrile (AIBN) are weighed as an initiator, two substances are added into the ethylene glycol dimethyl ether, stirring is carried out at 400rpm uniformly, a mixed material solution is obtained, then a porous current collector coated with active substances is soaked in the prepared solution, after 2min, the positive electrode plate is taken out and placed in a heating table at 70 ℃ for 10h, and the solid-state battery positive electrode plate is obtained.
Example 2
The embodiment provides a solid-state battery positive electrode plate, which is prepared by the following steps:
(1) 9g of LiNi is weighed 0.8 Mn 0.1 Co 0.1 O 2 (NMC 811), 1g of conductive carbon black super P and 1g of PVDF, adding the materials into NMP solution, uniformly stirring at a rotation speed of 400rpm to obtain homogeneous slurry, putting the slurry into a vacuum deaerator for deaeration treatment, then coating the slurry with bubbles removed on a porous foam aluminum current collector by using a scraper, and drying the porous foam aluminum current collector in a vacuum drying oven at 90 ℃ for 12 hours to obtain the porous current collector coated with active substances;
(2) In a glove box (O) 2 ≤0.01ppm、H 2 10g of 1, 3-Dioxolane (DOL) is weighed out and 0.152g of lithium hexafluorophosphate (LiPF) is weighed out simultaneously 6 ) Adding 2.87g LiTFSI serving as an open-loop initiator into DOL, stirring uniformly at 400rpm to obtain a mixed material solution, soaking the porous current collector coated with the active substance in the prepared solution, taking out the positive electrode plate after 2min, and placing the positive electrode plate on a heating table at 60 ℃ for 30h to obtain the positive electrode plate of the solid-state battery.
Example 3
The embodiment provides a solid-state battery positive electrode plate, which is prepared by the following steps:
(1) 9g of LiNi is weighed 0.8 Mn 0.1 Co 0.1 O 2 (NMC 811), 1g of conductive carbon black super P and 1g of PVDF, adding the materials into NMP solution, uniformly stirring at a rotation speed of 400rpm to obtain homogeneous slurry, putting the slurry into a vacuum deaerator for deaeration treatment, then coating the slurry with bubbles removed on a porous foam aluminum current collector by using a scraper, and drying the porous foam aluminum current collector in a vacuum drying oven at 90 ℃ for 12 hours to obtain the porous current collector coated with active substances;
(2) In a glove box (O) 2 ≤0.01ppm、H 2 O is less than or equal to 0.01 ppm), 7g of ethylene glycol diacrylate is measured, 1.5g of lithium hexafluoroborate and 0.006g of benzoyl peroxide are weighed as an initiator, two substances are added into the ethylene glycol diacrylate and uniformly stirred at 400rpm to obtain a mixed material solution, then the porous current collector coated with the active substances is soaked in the prepared solution, and after 2min, the positive electrode plate is taken out and placed on a heating table at 80 ℃ for 5h, so that the positive electrode plate of the solid-state battery is obtained.
Example 4
This example differs from example 1 only in that the mass of ethylene glycol dimethyl ether was 4.5g, and the other conditions and parameters were exactly the same as in example 1.
Example 5
This example differs from example 1 only in that the mass of ethylene glycol dimethyl ether was 27g, and the other conditions and parameters were identical to those of example 1.
Example 6
This example differs from example 1 only in that the mass of lithium bistrifluoromethylsulfonylimide is 0.6g, and the other conditions and parameters are exactly the same as in example 1.
Example 7
This example differs from example 1 only in that the mass of lithium bistrifluoromethylsulfonylimide is 6g, and the other conditions and parameters are exactly the same as in example 1.
Comparative example 1
The comparative example provides a positive electrode plate of a solid-state battery, and the preparation method of the positive electrode plate of the solid-state battery is as follows:
(1) 0.414g of zirconium n-propoxide solution and 0.5256g of lithium methoxide solution are respectively weighed in a glove box (H2O is less than or equal to 0.01ppm O2 is less than or equal to 0.01 ppm) and dissolved in 20ml of isopropanol solution to obtain coated precursor solution, 10g of NMC811 is weighed and added into the prepared coated precursor solution, the mixture is stirred for 5 hours at 400rpm and 70 ℃ to evaporate the solvent, then the mixture is placed into a vacuum drying box and dried for 10 hours at 80 ℃ to achieve the effect of complete solvent removal, and the pre-sintered LiZrO is obtained 3 The coated NMC811 anode material is placed in a tube furnace to be sintered for 5 hours at 300 ℃, and high-purity oxygen is introduced to obtain LiZrO 3 Coating and putting NMC811 anode material, marked as LiZrO 3 @NMC811。
(2) 9g of LiZrO was weighed 3 And (2) dissolving 811 @ NMC, 0.1g conductive carbon black Super P and 0.1g PVDF in a certain amount of NMP solution, uniformly stirring at a rotation speed of 400rpm to obtain homogeneous slurry, putting the slurry into a vacuum deaerator for deaeration treatment, coating the slurry with bubbles removed on a carbon-coated aluminum foil by using a scraper, and drying the carbon-coated aluminum foil in a vacuum drying oven at 90 ℃ for 10 hours to obtain the solid-state battery anode plate.
Comparative example 2
The comparative example provides a positive electrode plate of a solid-state battery, and the preparation method of the positive electrode plate of the solid-state battery is as follows:
(1) Coating an aluminum oxide coating layer with the thickness of 2.5nm on NMC811 anode material by adopting an atomic mechanical deposition (ALD) technology, and marking the material as Al 2 O 3 The @ NMC811 was then placed in a tube furnace and sintered at 500℃for 10 hours while fully introducing high purity oxygen.
(2) Weigh 9g Al 2 O 3 And (2) dissolving 811 @ NMC, 0.1g conductive carbon black Super P and 0.1g PVDF in a certain amount of NMP solution, uniformly stirring at a rotation speed of 400rpm to obtain homogeneous slurry, putting the slurry into a vacuum deaerator for deaeration treatment, coating the slurry with bubbles removed on a carbon-coated aluminum foil by using a scraper, and drying the carbon-coated aluminum foil in a vacuum drying oven at 90 ℃ for 10 hours to obtain the solid-state battery anode plate.
Comparative example 3
This comparative example differs from example 1 only in that the step (2) in-situ polymerization treatment was not performed, and other conditions and parameters were exactly the same as those of example 1.
Performance test:
positive electrode sheets prepared in examples 1 to 7 and comparative examples 1 to 3 were assembled into all solid-state mold batteries. The specific assembly process is as follows: cutting the prepared positive electrode plate into small wafers with the diameter of 10mm by a punching machine, assembling the small wafers with sulfide solid electrolyte and lithium indium negative electrode into an all-solid-state battery, and placing the all-solid-state battery into a blue battery test system for electrochemical performance test under the 0.1C multiplying power, wherein the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, according to examples 1 to 3, the initial-cycle discharge specific capacity of the solid-state battery positive electrode sheet prepared into a battery at 0.1C can be more than 199.8mAh/g, the capacity retention rate after 100 weeks can be more than 99.5%, and the capacity retention rate after 500 weeks can be more than 92%.
As can be seen from comparison of examples 1 and 4-5, in the preparation process of the solid-state battery positive electrode sheet, the addition amount of the polymer precursor influences the performance, the mass ratio of the polymer precursor to the positive electrode active material is controlled to be 1-2:1, the prepared positive electrode sheet has better performance, if the addition amount of the polymer precursor is too large, the too thick polymer layer leads to slower lithium ion transmission, further leads to lower discharge specific capacity, but the cycle retention rate is improved, and if the addition amount of the polymer precursor is too small, the too small polymer corresponds to a thinner coating layer thickness, the contact between the positive electrode material and sulfide electrolyte cannot be effectively avoided, so the effect is weak.
As can be seen from comparison of examples 1 and examples 6 to 7, in the preparation process of the positive electrode sheet of the solid-state battery, the addition amount of the lithium salt affects the performance, the mass ratio of the lithium salt to the polymer precursor is controlled to be 1-1.5:3, the prepared positive electrode sheet has better performance, if the addition amount of the lithium salt is too large, more lithium salt ensures the transmission of lithium ions, but too much lithium salt can generate a large amount of side reaction in the circulation process, so that the circulation performance is poor, and if the addition amount of the lithium salt is too small, less lithium salt causes weak energy for transmitting lithium ions, so that the discharge specific volume angle is caused.
The comparison of the example 1 and the comparative examples 1-2 shows that the conventional positive electrode material is coated directly, and then the positive electrode material is made into a battery, although the capacity performance and the cycle performance of the high-nickel positive electrode material in the all-solid-state battery can be improved to a certain extent, the capacity retention rate is obviously reduced after the cycle times are increased, and the capacity retention rate is still more than 90% after 500 weeks of cycle of the positive electrode plate prepared by the method disclosed by the application, so that the improvement effect is very obvious.
The application adopts an in-situ polymerization mode to coat a polymer layer on the surface of the positive electrode material in situ, thereby effectively isolating the direct contact between the positive electrode material and the solid electrolyte layer and obviously improving the electrochemical performance of the positive electrode material in the solid battery.
The applicant declares that the above is only a specific embodiment of the present application, but the scope of the present application is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present application disclosed by the present application fall within the scope of the present application and the disclosure.

Claims (10)

1. The preparation method of the solid-state battery positive electrode plate is characterized by comprising the following steps of:
(1) Mixing an anode active material, a conductive agent, a binder and a solvent to obtain slurry, and coating the slurry on the surface of a porous current collector to obtain the porous current collector coated with the active material;
(2) And mixing the polymer precursor, the initiator and the lithium salt to obtain a mixed material solution, arranging the mixed material solution on the surface and/or inside of the porous current collector coated with the active material, and carrying out in-situ polymerization reaction to obtain the solid-state battery anode plate.
2. The method of manufacturing according to claim 1, wherein the positive electrode active material of step (1) comprises any one or a combination of at least two of lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium cobalt oxide, and lithium manganate;
preferably, the conductive agent comprises any one or a combination of at least two of acetylene black, ketjen black, conductive carbon black, carbon nanotubes or graphene;
preferably, the binder comprises any one or a combination of at least two of polyvinylidene fluoride, guar gum, sodium alginate or carboxymethyl cellulose;
preferably, the solvent comprises any one or a combination of at least two of N-methylpyrrolidone, N-dimethylacetamide, acetonitrile or xylene.
3. The method of making according to claim 1 or 2, wherein the porous current collector of step (1) comprises porous aluminum foam;
preferably, the thickness of the porous current collector is 0.3-0.8 mm.
4. A method of preparation according to any one of claims 1 to 3, wherein the porous current collector of step (1) is pre-treated prior to coating;
preferably, the pretreatment comprises immersing the porous current collector in concentrated nitric acid, reacting for 10 hours at 120 ℃, cooling, washing with absolute ethanol, and drying.
5. The method of any one of claims 1-4, wherein the polymer precursor of step (2) comprises any one or a combination of at least two of ethylene glycol dimethyl ether, ethylene glycol methyl ether acrylate, 1.3-dioxolane, ethylene glycol diacrylate, or triethylene glycol dimethacrylate;
preferably, the initiator comprises benzoyl peroxide and/or azobisisobutyronitrile;
preferably, the lithium salt comprises any one or a combination of at least two of lithium bis (fluoromethylsulfonimide), lithium bis (trifluoromethylsulfonimide), lithium hexafluoroborate, lithium hexafluorophosphate or lithium perchlorate.
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the polymer precursor to the positive electrode active material in step (2) is (0.5 to 3): 1, preferably (1 to 2): 1.
7. The process according to any one of claims 1 to 6, wherein the mass ratio of the polymer precursor and the initiator in step (2) is 1 (0.001 to 0.005);
preferably, the mass ratio of the lithium salt to the polymer precursor is (1 to 1.5): 3.
8. The method of any one of claims 1 to 7, wherein the means of disposing in step (2) comprises dropping and/or injecting the mixture solution into the active material coated porous current collector or directly immersing the active material coated porous current collector into the mixture solution;
preferably, the temperature of the in-situ polymerization reaction is 60-80 ℃;
preferably, the in-situ polymerization reaction time is 5 to 30 hours.
9. A solid state battery positive electrode sheet, characterized in that it is produced by the method according to any one of claims 1-8.
10. An all-solid-state battery comprising the solid-state battery positive electrode sheet according to claim 9.
CN202310805619.9A 2023-07-03 2023-07-03 Positive electrode plate of solid-state battery and preparation method thereof Pending CN116825947A (en)

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Publication number Priority date Publication date Assignee Title
CN117117089A (en) * 2023-10-23 2023-11-24 浙江帕瓦新能源股份有限公司 Positive electrode of sodium ion battery, preparation method of positive electrode and sodium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117117089A (en) * 2023-10-23 2023-11-24 浙江帕瓦新能源股份有限公司 Positive electrode of sodium ion battery, preparation method of positive electrode and sodium ion battery
CN117117089B (en) * 2023-10-23 2024-03-19 浙江帕瓦新能源股份有限公司 Positive electrode of sodium ion battery, preparation method of positive electrode and sodium ion battery

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