CN113437249A - All-solid-state lithium battery composite positive electrode prepared based on melt infiltration method and preparation method thereof - Google Patents

All-solid-state lithium battery composite positive electrode prepared based on melt infiltration method and preparation method thereof Download PDF

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CN113437249A
CN113437249A CN202110729893.3A CN202110729893A CN113437249A CN 113437249 A CN113437249 A CN 113437249A CN 202110729893 A CN202110729893 A CN 202110729893A CN 113437249 A CN113437249 A CN 113437249A
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positive electrode
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娄帅锋
孙业财
王家钧
马玉林
尹鸽平
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Harbin Institute of Technology
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0473—Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals
    • H01M4/0476—Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals with molten 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
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Abstract

The invention discloses an all-solid-state lithium battery composite positive electrode prepared based on a permeation method and a preparation method thereof, and relates to the technical field of all-solid-state lithium batteries. The all-solid-state lithium battery positive electrode is a composite positive electrode obtained based on a melt infiltration method. In the present invention, Li of high ionic conductivity obtained by calcining1+xOHBrxAnd melting and permeating the mixture into the pores of the positive pole piece under the heating condition to obtain the composite positive pole. The composite anode has compact and uniform surface and extremely low porosity, and can form a solid electrolyte with good contactThe solid interface is fixed, so that the solid-solid contact area is increased, a stable and quick lithium ion channel is provided, the interface resistance is reduced, and finally the performance of the solid battery is obviously improved.

Description

All-solid-state lithium battery composite positive electrode prepared based on melt infiltration method and preparation method thereof
Technical Field
The invention relates to the technical field of all-solid-state lithium batteries, in particular to an all-solid-state lithium battery composite positive electrode prepared based on a melt infiltration method and a preparation method thereof.
Background
Lithium ion batteries, which are the most mainstream electrochemical energy storage devices at present, are not only widely applied to portable electronic products, but also are receiving more and more attention in the industries of electric vehicles and new energy resources. However, the traditional commercial lithium ion battery adopts organic liquid as electrolyte, has the problems of flammability, easy corrosion and the like, and seriously restricts the development of the lithium ion battery. In addition, lithium dendrites generated by the uneven deposition of negative electrode lithium metal may pierce the separator during battery cycling, resulting in short circuit of the battery, leakage of electrolyte, and combustion, which causes serious safety problems. Solid-state batteries mostly adopt nonflammable inorganic solid-state electrolytes to replace organic electrolytes, and can fundamentally solve the safety problem of the traditional liquid-state lithium ion batteries. And the solid electrolyte can be matched with a metal lithium cathode, so that the lithium ion battery has higher energy density. Therefore, the all-solid-state lithium battery with high safety and high energy density is expected to become the next generation advanced energy storage battery.
Although all-solid-state lithium batteries have many advantages, all-solid-state lithium batteries also have some problems to be solved. Wherein the problem of electrolyte/electrode interface has become a big bottleneck restricting the development of solid-state batteries. The electrolyte in the solid-state battery forms a solid-solid interface with the positive pole piece and the negative pole piece. The solid-solid contact is different from the solid-liquid contact existing in a soaking mode in the traditional liquid lithium ion battery, the solid-solid contact is a contact which is difficult to be fully attached, and the problems of small solid-solid contact area, increased interface impedance, reduced contact interface lithium ion access and the like are caused due to the lack of fluidity of a solid electrolyte.
Based on the advantages and disadvantages of the solid-state battery and the existing problems, it is very necessary to invent a preparation method of an all-solid-state lithium battery anode which can reduce the interface resistance of the solid-state battery, improve the solid-solid interface contact and improve the chemical stability of the interface.
Disclosure of Invention
The first purpose of the invention is to provide a composite positive electrode of an all-solid-state lithium battery, which aims to solve the problems of large interface resistance and poor solid-solid interface contact of the all-solid-state lithium battery;
the second purpose of the invention is to provide a method for preparing the composite positive electrode of the all-solid-state lithium battery based on a melt infiltration method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the composite positive electrode comprises a permeable layer, a positive electrode material layer and a current collector layer, wherein the positive electrode material layer is attached to the current collector layer, the permeable layer is attached to the positive electrode material layer and penetrates into the positive electrode material layer, and the permeable layer comprises Li1+xOHBrxWherein x is greater than 0.
Further, the Li1+xOHBrxThe preparation method comprises the following steps: taking an organic solvent I as a dispersion medium, fully ball-milling and mixing LiBr and LiOH to obtain a mixture, drying the mixture to obtain a precursor, calcining the precursor in a tube furnace under an inert atmosphere, and cooling to normal temperature to obtain Li1+xOHBrxWherein x is greater than 0.
Further, the molar ratio of the LiBr to the LiOH is 1:10-1: 1.
Further, the organic solvent I is one or a combination of carbon tetrachloride, dimethylformamide, toluene and pentane.
Furthermore, the calcining temperature of the tubular furnace calcining treatment is 350-1000 ℃, and the calcining time is 1-24 h.
Further, the positive electrode material layer includes a positive electrode active material, a conductive agent, and a binder.
Further, the positive electrode active material is one of lithium iron phosphate, lithium cobaltate, lithium manganate and lithium nickel cobalt manganese oxide, the binder is one of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO) and Polyacrylonitrile (PAN), and the conductive agent is one of acetylene black and carbon nanotubes.
Furthermore, the positive electrode active substance accounts for 50-96% of the total mass of the positive electrode material layer, the conductive agent accounts for 2-25% of the total mass of the positive electrode material layer, and the binder accounts for 2-25% of the total mass of the positive electrode material layer.
A method for preparing an all-solid-state lithium battery composite positive electrode based on a melt infiltration method comprises the following steps:
weighing LiBr and LiOH according to a certain proportion, fully ball-milling and mixing the two substances by taking an organic solvent I as a dispersion medium to obtain a mixture, drying the mixture to obtain a precursor, calcining the precursor in a tube furnace under an inert atmosphere, and cooling to normal temperature to obtain Li1+xOHBrxWherein x is greater than 0;
dispersing the positive active substance, the conductive agent and the binder in an organic solvent II according to a certain proportion to obtain positive slurry, coating the positive slurry on a positive current collector, and drying, rolling and punching to obtain a positive pole piece;
thirdly, placing the positive pole piece obtained in the second step on a heater in the atmosphere of nitrogen or inert gas, and placing the Li obtained in the first step1+xOHBrxUniformly dispersing the Li on the positive plate, and heating to make the Li1+xOHBrxMelting and permeating into the pores of the positive pole piece, and heating until solid Li1+xOHBrxAnd (4) closing the heater after complete melting, and cooling to room temperature to obtain the all-solid-state lithium battery composite anode.
Further, in the third step, the heating temperature is 250-300 ℃, and the heating time is 10-60 min.
Compared with the prior art, the invention has the beneficial effects that:
1) in the present invention, Li having a low melting point and high ionic conductivity is subjected to melt infiltration1+xOHBrxThe positive electrode material layer is penetrated and a permeable layer is formed on the positive electrode material layer, so that a compact, uniform and low-porosity composite positive electrode piece is formed, the chemical stability, the thermal stability and the mechanical stability of electrode components are favorably maintained, and the uniformity,The composite anode with extremely low porosity and the solid electrolyte can form a solid-solid interface with good contact, thereby increasing the solid-solid contact area, providing a stable and rapid lithium ion channel, reducing the interface resistance and finally obviously improving the performance of the solid battery.
2) The method has the advantages of simple operation, low cost and low equipment requirement, and is suitable for large-scale production.
3) The invention provides a new idea for preparing the all-solid-state battery and is beneficial to commercialization of the all-solid-state battery.
Drawings
Fig. 1 is a schematic structural diagram of an all-solid-state lithium battery composite positive electrode prepared based on a melt infiltration method.
Fig. 2 is a cycle performance chart of the all solid-state lithium ion battery positive electrode prepared in example 1 at 0.2C when applied to a solid-state battery.
Detailed Description
The invention is further illustrated by the following description and examples in conjunction with figures 1-2.
The first embodiment is as follows:
the utility model provides a compound positive pole of all solid-state lithium battery based on preparation of melting infiltration method, includes permeable formation 1, anodal material layer 2 and current collector layer 3, anodal material layer 2 is attached to on current collector layer 3, permeable formation 1 is attached to on anodal material layer 2 to the infiltration is in anodal material layer 2, permeable formation 1 includes high ionic conductivity Li1+xOHBrxWherein x is greater than 0.
Further, the Li1+xOHBrxThe preparation method comprises the following steps: weighing LiBr and LiOH according to a certain proportion, fully ball-milling and mixing the two substances by taking an organic solvent I as a dispersion medium to obtain a mixture, drying the mixture to obtain a precursor, calcining the precursor in a tube furnace under an inert atmosphere, naturally cooling to normal temperature to obtain Li1+xOHBrxWherein x is greater than 0.
Further, the molar ratio of the LiBr to the LiOH is 1:10-1: 1.
Further, the organic solvent I is one or more of carbon tetrachloride, dimethylformamide, toluene and pentane.
Furthermore, the ball milling speed is 100-.
Further, the drying temperature of the mixture is 80-150 ℃, and the drying time is 10-30 hours.
Furthermore, the calcining temperature of the tubular furnace calcining treatment is 350-1000 ℃, and the calcining time is 1-24 hours.
Further, the positive electrode material layer includes a positive electrode active material, a conductive agent, and a binder.
Further, the positive electrode active material is one of lithium iron phosphate, lithium cobaltate, lithium manganate and lithium nickel cobalt manganese oxide, the binder is one of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO) and Polyacrylonitrile (PAN), and the conductive agent is one of acetylene black and carbon nanotubes.
Furthermore, the positive electrode active substance accounts for 50-96% of the total mass of the positive electrode material layer, the conductive agent accounts for 2-25% of the total mass of the positive electrode material layer, and the binder accounts for 2-25% of the total mass of the positive electrode material layer.
The second embodiment is as follows:
a method for preparing an all-solid-state lithium battery composite positive electrode based on a melt infiltration method comprises the following steps:
weighing LiBr and LiOH according to a certain proportion, fully ball-milling and mixing the two substances by taking an organic solvent I as a dispersion medium to obtain a mixture, drying the mixture to obtain a precursor, calcining the precursor in a tube furnace under an inert atmosphere, naturally cooling to normal temperature to obtain Li with an anti-perovskite structure1+xOHBrxWherein x is greater than 0;
dispersing the positive active substance, the conductive agent and the binder in an organic solvent II according to a certain proportion to obtain positive slurry, coating the positive slurry on a positive current collector, drying, rolling and punching to obtain a positive pole piece;
step three, in the atmosphere of nitrogen or inert gas, the step twoPlacing the obtained positive pole piece on a heater, and placing the Li obtained in the step one1+xOHBrxUniformly dispersing the Li on the positive plate, and heating to make the Li1+xOHBrxMelting and permeating into the pores of the positive pole piece, and heating until solid Li1+xOHBrxAfter complete melting, the heater is closed, and the mixture is naturally cooled to room temperature to obtain a compact all-solid-state lithium battery composite anode with good contact and low interface impedance;
further, the molar ratio of LiBr to LiOH in the first step is 1:10-1: 1.
Further, in the first step, the organic solvent I is one or a combination of carbon tetrachloride, Dimethylformamide (DMF), toluene and pentane.
Further, in the step one, the ball milling rotation speed is 100-.
Further, in the step one, the drying temperature of the mixture is 80-150 ℃, and the drying time is 10-30 hours.
Further, in the first step, the calcination temperature of the tubular furnace is 350-.
Preferably, in the second step, the positive electrode active material is one of lithium iron phosphate, lithium cobaltate, lithium manganate and lithium nickel cobalt manganese, the binder is one of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO) and Polyacrylonitrile (PAN), and the conductive agent is one of acetylene black and carbon nanotubes.
Furthermore, in the second step, the positive electrode active substance accounts for 50-96% of the positive electrode material layer, the conductive agent accounts for 2-25% of the positive electrode material layer, and the binder accounts for 2-25% of the positive electrode material layer.
Preferably, in the second step, the organic solvent II is N-methylpyrrolidone (NMP).
Further, in the third step, the heating temperature is 250-300 ℃, and the heating time is 10-60 minutes.
Further, in the third step, Li is uniformly dispersed on a single pole piece with the diameter of 14mm1+xOHBrxThe mass of (A) is 2-4 mg.
Example 1
A method for preparing an all-solid-state lithium battery composite positive electrode based on a melt infiltration method comprises the following steps:
weighing LiBr and LiOH according to a molar ratio of LiBr to LiOH of 7:10, taking methylbenzene as a dispersion medium, performing ball milling for 15 hours at 500 revolutions per minute on a ball mill, fully performing ball milling and mixing to obtain a mixture, performing vacuum drying on the mixture for 15 hours at 120 ℃ to obtain a precursor, calcining the precursor for 20 hours at 600 ℃ under an inert atmosphere, and naturally cooling to normal temperature to obtain Li with an anti-perovskite structure1.7OHBr0.7；
Step two, LiNi is used0.8Co0.1Mn0.1O2Dispersing a positive electrode active substance, acetylene black as a conductive agent and PVDF as a binder in NMP according to the mass ratio of 8:1:1 to obtain positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, drying, rolling and punching to obtain a positive electrode piece with the diameter of 14 mm;
thirdly, placing the positive pole piece obtained in the second step on a heater in the atmosphere of nitrogen or inert gas, and respectively placing 3mg of Li obtained in the first step1.7OHBr0.7Uniformly dispersing on each positive plate with a diameter of 14mm, heating to 300 ℃, and heating for 20 minutes to enable Li to be uniformly dispersed on each positive plate1.7OHBr0.7The molten material permeates into the pores of the positive pole piece to obtain a compact, good-contact and low-interface-impedance all-solid-state lithium battery composite positive pole;
example 2
A method for preparing an all-solid-state lithium battery anode based on a melt infiltration method comprises the following steps:
weighing LiBr and LiOH according to a molar ratio of LiBr to LiOH 1:1, taking DMF as a dispersion medium, performing ball milling for 12 hours at 800 rpm on a ball mill, fully performing ball milling and mixing to obtain a mixture, performing vacuum drying on the mixture at 150 ℃ for 12 hours to obtain a precursor, calcining the precursor at 650 ℃ for 18 hours under an inert atmosphere, and naturally cooling to normal temperature to obtain Li with an anti-perovskite structure2OHBr；
Dispersing lithium iron phosphate serving as a positive electrode active substance, a carbon nano tube serving as a conductive agent and PEO serving as a binder in NMP according to the mass ratio of 7:2:1 to obtain positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, drying, rolling and punching to obtain a positive electrode piece with the diameter of 14 mm;
step three, placing the positive pole piece obtained in the step two on a heater in the atmosphere of nitrogen or inert gas, and respectively placing 4mg of Li obtained in the step one2OHBr is uniformly dispersed on each positive plate with the diameter of 14mm, heated to 290 ℃ for 25 minutes to enable Li2The OHBr is melted and permeated into the pores of the positive pole piece to obtain the compact, well-contacted and low-interface-impedance all-solid-state lithium battery composite positive pole;
example 3
A method for preparing an all-solid-state lithium battery anode based on a melt infiltration method comprises the following steps:
weighing LiBr and LiOH according to a molar ratio of LiBr to LiOH of 3:10, taking carbon tetrachloride as a dispersion medium, performing ball milling on the mixture for 18 hours at a speed of 600 revolutions per minute in a ball mill, sufficiently performing ball milling and mixing to obtain a mixture, performing vacuum drying on the mixture for 24 hours at a temperature of 100 ℃ to obtain a precursor, calcining the precursor for 24 hours at a temperature of 550 ℃ in an inert atmosphere, and naturally cooling to normal temperature to obtain Li with an anti-perovskite structure1.3OHBr0.3；
Step two, LiCoO is used2Dispersing a positive electrode active substance, acetylene black as a conductive agent and PVDF as a binder in NMP according to the mass ratio of 9:0.5:0.5 to obtain positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, drying, rolling and punching to obtain a positive electrode piece with the diameter of 14 mm;
thirdly, placing the positive pole piece obtained in the second step on a heater in the atmosphere of nitrogen or inert gas, and respectively placing 2mg of Li obtained in the first step1.3OHBr0.3Uniformly dispersing the lithium ion battery anode material on each positive plate with the diameter of 14mm, heating to 280 ℃ for 30 minutes to enable the lithium ion battery anode material to be Li1.3OHBr0.3The molten material permeates into the pores of the positive pole piece to obtain a compact, good-contact and low-interface-impedance all-solid-state lithium battery composite positive pole;
example 4
A method for preparing an all-solid-state lithium battery anode based on a melt infiltration method comprises the following steps:
weighing LiBr and LiOH according to a molar ratio of LiBr to LiOH 1:2, taking pentane as a dispersion medium, performing ball milling on the mixture for 10 hours at 1000 revolutions per minute in a ball mill, fully performing ball milling and mixing to obtain a mixture, performing vacuum drying on the mixture for 30 hours at 80 ℃ to obtain a precursor, calcining the precursor for 20 hours at 700 ℃ in an inert atmosphere, and naturally cooling to normal temperature to obtain Li with an anti-perovskite structure1.5OHBr0.5；
Step two, LiNi is used0.6Co0.2Mn0.2O2Dispersing a positive electrode active substance, acetylene black as a conductive agent and PVDF as a binder in NMP according to the mass ratio of 8:1:1 to obtain positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, drying, rolling and punching to obtain a positive electrode piece with the diameter of 14 mm;
step three, placing the positive pole piece obtained in the step two on a heater in the atmosphere of nitrogen or inert gas, and respectively placing 4mg of Li obtained in the step one1.5OHBr0.5Uniformly dispersing the lithium ion battery anode material on each anode plate with the diameter of 14mm, heating to 290 ℃, and heating for 30 minutes to enable the lithium ion battery anode material to be Li1.5OHBr0.5The molten material permeates into the pores of the positive pole piece to obtain a compact, good-contact and low-interface-impedance all-solid-state lithium battery composite positive pole;
fig. 2 is a cycle performance chart of the all solid-state lithium ion battery positive electrode prepared in example 1 at 0.2C when applied to a solid-state battery. Example 1 all-solid-state battery test operating conditions were as follows: the working temperature is 45 ℃, the charge-discharge multiplying power is 0.2C, and the charge-discharge voltage interval is 3.0-4.2V.
The cycle performance of the all solid-state lithium battery in fig. 2 shows: the coulombic efficiency of the battery except for the first cycle is more than 99.4%, and the capacity retention rate after the first 50 cycles is 89%. Therefore, a compact and uniform composite anode plate with extremely low porosity can be formed by a melt infiltration method, the chemical stability, the thermal stability and the mechanical stability of electrode components are improved, and the uniform and extremely low porosity composite anode and a solid electrolyte can form a solid-solid interface with good contact, so that the solid-solid contact area is increased, a stable and rapid lithium ion channel is provided, the interface resistance is reduced, and finally the performance of the solid battery is obviously improved.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. But all technical solutions formed by adopting equal or equivalent transformations fall within the protection scope of the claims of the present invention.

Claims (10)

1. The composite positive electrode is characterized by comprising a permeable layer (1), a positive electrode material layer (2) and a current collector layer (3), wherein the positive electrode material layer (2) is attached to the current collector layer (3), the permeable layer (1) is attached to the positive electrode material layer (2) and permeates into the positive electrode material layer (2), and the permeable layer (1) comprises Li1+xOHBrxWherein x is greater than 0.
2. The all-solid-state lithium battery composite positive electrode according to claim 1, wherein the Li1+xOHBrxThe preparation method comprises the following steps: taking an organic solvent I as a dispersion medium, fully ball-milling and mixing LiBr and LiOH to obtain a mixture, drying the mixture to obtain a precursor, calcining the precursor in a tube furnace under an inert atmosphere, and cooling to normal temperature to obtain Li1+ xOHBrxWherein x is greater than 0.
3. The all-solid-state lithium battery composite positive electrode according to claim 2, characterized in that: the molar ratio of LiBr to LiOH is 1:10-1: 1.
4. The all-solid-state lithium battery composite positive electrode according to claim 2, characterized in that: the organic solvent I is one or a combination of carbon tetrachloride, dimethylformamide, toluene and pentane.
5. The all-solid-state lithium battery composite positive electrode according to claim 2, characterized in that: the calcining temperature of the tubular furnace calcining treatment is 350-1000 ℃, and the calcining time is 1-24 h.
6. The all-solid-state lithium battery composite positive electrode according to claim 1, characterized in that: the positive electrode material layer includes a positive electrode active material, a conductive agent, and a binder.
7. The all-solid-state lithium battery composite positive electrode according to claim 6, characterized in that: the positive electrode active material is one of lithium iron phosphate, lithium cobaltate, lithium manganate and nickel cobalt lithium manganate, the binder is one of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO) and Polyacrylonitrile (PAN), and the conductive agent is one of acetylene black and carbon nano tubes.
8. The all-solid-state lithium battery composite positive electrode according to claim 6, characterized in that: the positive electrode active substance accounts for 50-96% of the total mass of the positive electrode material layer, the conductive agent accounts for 2-25% of the total mass of the positive electrode material layer, and the binder accounts for 2-25% of the total mass of the positive electrode material layer.
9. A method for preparing the all-solid-state lithium battery composite positive electrode according to any one of claims 1 to 8, comprising the steps of:
weighing LiBr and LiOH according to a certain proportion, fully ball-milling and mixing the two substances by taking an organic solvent I as a dispersion medium to obtain a mixture, drying the mixture to obtain a precursor, calcining the precursor in a tube furnace under an inert atmosphere, and cooling to normal temperature to obtain Li1+xOHBrxWherein x is greater than 0;
dispersing the positive active substance, the conductive agent and the binder in an organic solvent II according to a certain proportion to obtain positive slurry, coating the positive slurry on a positive current collector, and drying, rolling and punching to obtain a positive pole piece;
thirdly, placing the positive pole piece obtained in the second step on a heater in the atmosphere of nitrogen or inert gas, and placing the Li obtained in the first step1+xOHBrxUniformly dispersing the Li on the positive plate, and heating to make the Li1+xOHBrxMelting and permeating into the pores of the positive pole piece, and heating until solid Li1+xOHBrxAnd (4) closing the heater after complete melting, and cooling to room temperature to obtain the all-solid-state lithium battery composite anode.
10. The method for preparing the all-solid-state lithium battery composite positive electrode according to claim 9, characterized in that: in the third step, the heating temperature is 250-300 ℃, and the heating time is 10-60 min.
CN202110729893.3A 2021-06-29 2021-06-29 All-solid-state lithium battery composite positive electrode prepared based on melt infiltration method and preparation method thereof Pending CN113437249A (en)

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CN114373933A (en) * 2022-01-07 2022-04-19 北京胜能能源科技有限公司 Solid-state battery positive plate and preparation method thereof and solid-state battery

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CN111370751A (en) * 2018-12-25 2020-07-03 深圳市比亚迪锂电池有限公司 Solid-state battery, preparation method thereof and electric automobile
CN112768754A (en) * 2020-12-30 2021-05-07 南方科技大学 Solid electrolyte, preparation method thereof and all-solid-state battery

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CN105304931A (en) * 2014-07-23 2016-02-03 精工爱普生株式会社 Electrode assembly, lithium battery, and method for producing electrode assembly
CN111370751A (en) * 2018-12-25 2020-07-03 深圳市比亚迪锂电池有限公司 Solid-state battery, preparation method thereof and electric automobile
CN112768754A (en) * 2020-12-30 2021-05-07 南方科技大学 Solid electrolyte, preparation method thereof and all-solid-state battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114373933A (en) * 2022-01-07 2022-04-19 北京胜能能源科技有限公司 Solid-state battery positive plate and preparation method thereof and solid-state battery
CN114373933B (en) * 2022-01-07 2023-11-21 北京胜能能源科技有限公司 Solid-state battery positive plate, preparation method thereof and solid-state battery

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