CN115579526A - Solid-state battery and preparation method and application thereof - Google Patents
Solid-state battery and preparation method and application thereof Download PDFInfo
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- CN115579526A CN115579526A CN202211393677.7A CN202211393677A CN115579526A CN 115579526 A CN115579526 A CN 115579526A CN 202211393677 A CN202211393677 A CN 202211393677A CN 115579526 A CN115579526 A CN 115579526A
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- 239000003792 electrolyte Substances 0.000 claims abstract description 198
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
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- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- 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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- 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
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/13—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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a solid-state battery and a preparation method and application thereof, wherein the solid-state battery comprises: the positive plate comprises a positive current collector and a positive active material layer, wherein the positive active material layer comprises a positive active material, a first conductive agent, a first oxide electrolyte and a first binder; a positive electrode oxide electrolyte layer including a second oxide electrolyte and a second binder; a solid electrolyte layer; a negative oxide electrolyte layer including a third oxide electrolyte and a third binder; and the negative plate comprises a negative current collector and a negative active material layer, wherein the negative active material layer comprises a negative active material, a second conductive agent, a fourth oxide electrolyte and a fourth binder. The invention fundamentally solves the safety problem of the battery, improves the comprehensive electrical property of the lithium ion battery on the premise of ensuring the structural stability of the active material, and improves the electrical conductivity between the active material layer and the solid electrolyte layer.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a solid-state battery and a preparation method and application thereof.
Background
Aiming at the safety problem of the power battery, the safety problem is mainly influenced by three factors, namely oxygen, temperature and an ignition medium organic solvent, wherein the influence of the organic solvent is crucial, at present, a liquid electrolyte is adopted by the mainstream power battery, and the liquid electrolyte contains a large amount of organic solvent, so that the reduction of the content of the organic solvent or the avoidance of the application of the organic solvent becomes an effective way for improving the safety problem of the battery. At present, the semi-solid or solid battery is researched at home and abroad, and the safety problem of the power battery is fundamentally solved. Semi-solid or solid batteries have good high temperature resistance, while also having relatively good performance at low temperatures. Nowadays, solid-state batteries become an industrial research hotspot, and some enterprises realize mass production application of semi-solid-state batteries. However, the conductivity between the positive/negative electrode active material layers and the solid electrolyte layer in the solid-state battery is poor, resulting in poor overall electrical properties of the solid-state battery.
In addition, electrolytes used by solid-state batteries are mainly divided into three research systems, namely oxide electrolytes, sulfide electrolytes and polymer electrolytes, wherein domestic enterprises take oxide electrolytes as main research directions, japanese and Korean enterprises take sulfide electrolytes as main research directions, and European and American enterprises take polymer electrolytes as main research directions. Different advantages and disadvantages exist for different electrolyte systems, thereby influencing the application of the electrolyte systems. The oxide electrolyte is easy to prepare and apply, but the oxide electrolyte has high hardness, so that the contact between the electrolyte and an active material interface is influenced; the conductivity of the sulfide electrolyte can be comparable to that of liquid electrolyte, but the sulfide electrolyte has poor chemical stability, is easy to oxidize, is easy to generate harmful gases such as hydrogen sulfide and the like when meeting water, and has complex production and processing processes; the polymer electrolyte has high conductivity at high temperature, is easy to form a film, and has good compatibility with positive and negative electrodes, but the polymer electrolyte has the defects of low conductivity at normal temperature, low oxidation potential of the electrolyte, and the hidden trouble that lithium dendrite penetrates through the polymer film. In addition, some domestic enterprises develop semi-solid batteries at the same time, and part of liquid electrolyte is added into a solid electrolyte system, so that the safety performance of the batteries is slightly improved, but the safety problem cannot be fundamentally solved, and meanwhile, the high-temperature and low-temperature performance of the batteries is not obviously improved.
Disclosure of Invention
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the invention aims to provide a solid-state battery, and a preparation method and application thereof. The invention fundamentally solves the safety problem of the battery, improves the comprehensive electrical property of the lithium ion battery on the premise of ensuring the structural stability of the active material, and improves the electrical conductivity between the active material layer and the solid electrolyte layer.
To achieve the above object, in one aspect of the present invention, a solid-state battery is provided. According to an embodiment of the present invention, the solid-state battery includes:
the positive electrode plate comprises a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material, a first conductive agent, a first oxide electrolyte and a first binder;
a positive electrode oxide electrolyte layer disposed on a side of the positive electrode active material layer away from the positive electrode current collector, the positive electrode oxide electrolyte layer including a second oxide electrolyte and a second binder;
the solid electrolyte layer is arranged on one side of the positive electrode oxide electrolyte layer far away from the positive electrode sheet;
the negative electrode oxide electrolyte layer is arranged on one side, far away from the positive electrode oxide electrolyte layer, of the solid electrolyte layer and comprises a third oxide electrolyte and a third binder;
the negative pole piece, the negative pole piece includes negative pole mass flow body and negative active material layer, the negative active material layer sets up keeping away from on negative oxide electrolyte layer one side on solid state electrolyte layer, the negative pole mass flow body sets up keeping away from on the negative active material layer one side on negative oxide electrolyte layer, the negative active material layer includes negative active material, second conductive agent, fourth oxide electrolyte and fourth binder.
According to the solid-state battery of the embodiment of the invention, firstly, because the solid-state battery has no free organic solvent inside, the safety problem of the battery is fundamentally solved. And secondly, the conductive agent in the active material layer is compounded between the active material and the oxide electrolyte, and a perfect conductive network structure is formed around the active material particles, so that the electrochemical performance and the safety performance of the lithium ion battery are improved on the premise of ensuring the structural stability of the active material. Thirdly, the oxide electrolyte layers are respectively arranged on the positive plate and the negative plate to replace the diaphragm, so that the problem of short circuit caused by contact of the positive electrode material and the negative electrode material is solved, and the conductivity between the active material layer and the solid electrolyte layer is further improved.
In addition, the solid-state battery according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the present invention, the mass ratio of the positive electrode active material, the first conductive agent, and the first oxide electrolyte is 100 (0.1-10) to (3-20).
In some embodiments of the present invention, the thickness of the positive electrode active material layer is 150 to 450 μm.
In some embodiments of the present invention, the mass ratio of the second oxide electrolyte to the second binder is 100 (0.1 to 5).
In some embodiments of the present invention, the thickness of the positive electrode oxide electrolyte layer is 10 to 80 μm.
In some embodiments of the present invention, the solid electrolyte layer comprises a fifth oxide solid electrolyte, a polymer electrolyte, a lithium salt and an organic solvent, wherein the concentration of the lithium salt in the organic solvent is 2.5 to 4.5mol/L, preferably 3 to 4mol/L.
In some embodiments of the present invention, the mass ratio of the fifth oxide solid-state electrolyte, the polymer electrolyte, and the lithium salt is (0 to 1): (0.1-0.5): (0.8-1.2).
In some embodiments of the invention, the fifth oxide electrolyte is selected from at least one of garnet-type solid electrolytes, perovskite-type solid electrolytes, LISICON-type solid electrolytes, and NASICON-type solid electrolytes.
In some embodiments of the present invention, the monomers of the polymer electrolyte include butyl acrylate and glycerol.
In some embodiments of the invention, the lithium salt is selected from at least one of lithium bis fluorosulfonylimide, lithium bis trifluoromethylsulfonyl imide, and lithium bis oxalato borate.
In some embodiments of the invention, the organic solvent is selected from at least one of propylene carbonate, ethylene carbonate, butylene carbonate, ethylmethyl carbonate, dimethyl carbonate, and diethyl carbonate.
In some embodiments of the present invention, the mass ratio of the negative electrode active material, the second conductive agent, and the fourth oxide electrolyte is 100 (0.1-10) to (3-20).
In some embodiments of the present invention, the thickness of the anode active material layer is 200 to 500 μm.
In some embodiments of the present invention, the mass ratio of the third oxide electrolyte to the third binder is 100 (0.1-5).
In some embodiments of the invention, the thickness of the negative electrode oxide electrolyte layer is 10 to 80 μm.
In some embodiments of the invention, the positive active material is selected from at least one of ternary NCM materials and LFP materials.
In some embodiments of the present invention, the first oxide electrolyte, the second oxide electrolyte, the third oxide electrolyte, and the fourth oxide electrolyte are each independently selected from at least one of garnet-type solid state electrolytes, perovskite-type solid state electrolytes, LISICON-type solid state electrolytes, and NASICON-type solid state electrolytes.
In some embodiments of the present invention, the first conductive agent and the second conductive agent are each independently selected from at least one of graphene and graphene oxide.
In some embodiments of the present invention, the negative active material is selected from at least one of a graphite material, a hard carbon, a soft carbon, a silicon material, and a silicon carbon composite material.
In a second aspect of the invention, a method of making a solid-state battery is provided. According to an embodiment of the invention, the method comprises the steps of:
(1) Forming a positive electrode active material layer on a positive electrode current collector, the positive electrode active material layer including a positive electrode active material, a first conductive agent, a first oxide electrolyte, and a first binder;
(2) Forming a positive electrode oxide electrolyte layer on one side of the positive electrode active material layer far away from the positive electrode current collector, wherein the positive electrode oxide electrolyte layer comprises a second oxide electrolyte and a second binder;
(3) Forming a negative electrode active material layer on the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a second conductive agent, a fourth oxide electrolyte, and a fourth binder;
(4) Forming a negative electrode oxide electrolyte layer on one side of the negative electrode active material layer far away from the negative electrode current collector, wherein the negative electrode oxide electrolyte layer comprises a third oxide electrolyte and a third binder;
(5) A solid electrolyte layer is formed between the positive electrode oxide electrolyte layer and the negative electrode oxide electrolyte layer.
According to the method for preparing the solid-state battery provided by the embodiment of the invention, the prepared solid-state battery has no free organic solvent, so that the safety problem of the battery is fundamentally solved. Meanwhile, the conductive agent in the active material layer is compounded between the active material and the oxide electrolyte, and a perfect conductive network structure is formed around the active material particles, so that the comprehensive electrical property of the lithium ion battery is improved on the premise of ensuring the structural stability of the active material. In addition, according to the method, the oxide electrolyte layers are respectively prepared on the positive plate and the negative plate, so that the problem of short circuit caused by contact of the positive electrode material and the negative electrode material is solved by replacing a diaphragm, and the conductivity between the active material layer and the solid electrolyte layer is further improved.
In addition, the method of manufacturing a solid-state battery according to the above-described embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, step (1) comprises:
(1-1) mixing a positive electrode active material, a first conductive agent, a first oxide electrolyte and a first solvent, performing ball milling, and drying to obtain a composite positive electrode material;
(1-2) mixing the composite positive electrode material, the first binder and the second solvent to form positive electrode slurry, and coating the positive electrode slurry on a positive electrode current collector to form a positive electrode plate.
In some embodiments of the invention, step (3) comprises:
(3-1) mixing the negative electrode active material, the second conductive agent, the fourth oxide electrolyte and the third solvent, ball-milling and drying to obtain a composite negative electrode material;
(3-2) mixing the composite negative electrode material, a fourth binder and a fourth solvent to form negative electrode slurry, and coating the negative electrode slurry on a negative electrode current collector so as to form a negative electrode sheet.
In some embodiments of the invention, step (5) comprises:
(5-1) mixing a fifth oxide solid electrolyte, a polymer electrolyte monomer, an initiator, a lithium salt, and an organic solvent to obtain a liquid electrolyte;
(5-2) injecting the liquid electrolyte into a solid lithium ion battery, and carrying out polymerization reaction so as to obtain a solid electrolyte layer.
In some embodiments of the invention, the temperature of the polymerization reaction is 50 to 80 ℃ and the time of the polymerization reaction is 2 to 5 hours.
According to a third aspect of the invention, the invention proposes a vehicle having the above-described solid-state battery or the solid-state battery obtained by the above-described manufacturing method according to an embodiment of the invention. Compared with the prior art, the vehicle safety is higher, and the comprehensive electrical property of the battery is more excellent. It should be noted that the features and effects described above for the solid-state battery and the method for manufacturing the solid-state battery are also applicable to the vehicle, and are not described in detail herein.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural view of a solid-state battery according to an embodiment of the present invention;
the battery comprises a positive electrode collector 100, a positive electrode active material layer 200, a positive electrode oxide electrolyte layer 300, a solid electrolyte layer 400, a negative electrode oxide electrolyte layer 500, a negative electrode active material layer 600 and a negative electrode collector 700.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the invention, a solid-state battery is presented. According to an embodiment of the present invention, referring to fig. 1, a solid-state battery includes a positive electrode tab including a positive electrode current collector 100 and a positive electrode active material layer 200 formed on the positive electrode current collector 100, the positive electrode active material layer 200 including a positive electrode active material, a first conductive agent, a first oxide electrolyte, and a first binder; a positive electrode oxide electrolyte layer 300, the positive electrode oxide electrolyte layer 300 being disposed on a side of the positive electrode active material layer 200 away from the positive electrode current collector 100, the positive electrode oxide electrolyte layer 300 including a second oxide electrolyte and a second binder; a solid electrolyte layer 400, wherein the solid electrolyte layer 400 is arranged on the side of the positive electrode oxide electrolyte layer 300 far away from the positive electrode sheet; a negative oxide electrolyte layer 500, the negative oxide electrolyte layer 500 being disposed on a side of the solid electrolyte layer 400 remote from the positive oxide electrolyte layer 300, the negative oxide electrolyte layer 500 comprising a third oxide electrolyte and a third binder; the negative electrode sheet comprises a negative electrode current collector 700 and a negative electrode active material layer 600, the negative electrode active material layer 600 is arranged on one side of the negative electrode oxide electrolyte layer 500 far away from the solid electrolyte layer 400, the negative electrode current collector 700 is arranged on one side of the negative electrode active material layer 600 far away from the negative electrode oxide electrolyte layer 500, and the negative electrode active material layer 600 comprises a negative electrode active material, a second conductive agent, a fourth oxide electrolyte and a fourth binder. Therefore, because the solid-state battery has no free organic solvent inside, the safety problem of the battery is fundamentally solved. Meanwhile, the first conductive agent in the positive active material layer is compounded between the positive active material and the first oxide electrolyte, and a perfect conductive network structure is formed around the positive active material particles, so that the comprehensive electrical property of the lithium ion battery is improved on the premise of ensuring the structural stability of the positive active material; similarly, the second conductive agent in the negative active material layer is compounded between the negative active material and the fourth oxide electrolyte, and a perfect conductive network structure is formed around the negative active material particles, so that the comprehensive electrical property of the lithium ion battery is improved on the premise of ensuring the structural stability of the negative active material. In addition, the oxide electrolyte layers are respectively arranged on the positive plate and the negative plate, so that the problem of short circuit caused by contact of the positive electrode material and the negative electrode material is solved by replacing the diaphragm, and the conductivity between the active material layer and the solid electrolyte layer is further improved.
According to some embodiments of the invention, in the positive electrode active material layer, the mass ratio of the positive electrode active material, the first conductive agent and the first oxide electrolyte is 100 (0.1-10) to (3-20), so that the mass ratio of the positive electrode active material, the first conductive agent and the first oxide electrolyte is limited to the above range, and a perfect conductive network structure is further ensured to be formed around the positive electrode active material particles, thereby further improving the comprehensive electrical performance of the lithium ion battery on the premise of ensuring the structural stability of the positive electrode active material. Further, the thickness of the positive electrode active material layer is 150 to 450 μm.
According to still other embodiments of the present invention, in the positive electrode oxide electrolyte layer, the mass ratio of the second oxide electrolyte to the second binder is 100 (0.1 to 5), preferably 100 (0.5 to 3), whereby the mass ratio of the second oxide electrolyte to the second binder is limited to the above range, and the second oxide electrolyte can be effectively bonded while the contact between the second oxide particles is increased, facilitating the ion transport. Further, the thickness of the positive oxide electrolyte layer is 10 to 80 μm, preferably 20 to 50 μm, whereby the thickness of the positive oxide electrolyte layer is limited to the above range, the contact of the positive and negative electrodes is effectively avoided, and the ion transport distance is also reduced.
According to further specific embodiments of the present invention, in the negative electrode active material layer, the mass ratio of the negative electrode active material, the second conductive agent and the fourth oxide electrolyte is 100 (0.1-10) to (3-20), so that the mass ratio of the negative electrode active material, the second conductive agent and the fourth oxide electrolyte is limited to the above range, and a perfect conductive network structure is further ensured to be formed around the negative electrode active material particles, thereby further improving the comprehensive electrical performance of the lithium ion battery on the premise of ensuring the structural stability of the negative electrode active material. Further, the thickness of the anode active material layer is 200 to 500 μm.
According to still further embodiments of the present invention, in the negative electrode oxide electrolyte layer, the mass ratio of the third oxide electrolyte to the third binder is 100 (0.1-5), preferably 100 (0.5-3), so that the mass ratio of the third oxide electrolyte to the third binder is limited to the above range, thereby effectively bonding the third oxide electrolyte and increasing the contact between the third oxide particles to facilitate ion transport. Further, the thickness of the negative electrode oxide electrolyte layer is 10 to 80 μm, preferably 20 to 50 μm, whereby the thickness of the negative electrode oxide electrolyte layer is limited to the above range, the contact of the positive and negative electrodes is effectively avoided, and the ion transport distance is also reduced.
In the embodiment of the present invention, the specific kind of the above-mentioned cathode active material is not particularly limited, and as some specific examples, the cathode active material may be selected from at least one of ternary NCM material and LFP material. Also, the specific kind of the above-described anode active material is not particularly limited, and as some specific examples, the anode active material may be selected from at least one of a graphite material, hard carbon, soft carbon, a silicon material, and a silicon-carbon composite material.
In an embodiment of the present invention, specific kinds of the first conductive agent and the second conductive agent are not particularly limited, and as some specific examples, each of the first conductive agent and the second conductive agent may be independently selected from at least one of graphene and graphene oxide. Likewise, specific kinds of the above-described first oxide electrolyte, second oxide electrolyte, third oxide electrolyte and fourth oxide electrolyte are not particularly limited, and as some specific examples, each of the first oxide electrolyte, second oxide electrolyte, third oxide electrolyte and fourth oxide electrolyte independently may be selected from garnet-type Li 7 La 3 Zr 2 O 12 (LLZO), perovskite type, LISICON type and NASICON type solid electrolytes. The first adhesive, the second adhesive, the third adhesive and the fourth adhesive are conventional adhesives in the art, and the specific types thereof are not particularly limited.
According to still other embodiments of the present invention, the solid electrolyte layer includes a fifth oxide solid electrolyte, a polymer electrolyte, a lithium salt and an organic solvent, wherein the concentration of the lithium salt in the organic solvent is 2.5 to 4.5mol/L, preferably 3 to 4mol/L, so that the polymer electrolyte with good flexibility and the high-concentration lithium salt electrolyte with high conductivity improve the wettability between the fifth oxide electrolyte and the electrode material, reduce the contact internal resistance of the fifth oxide electrolyte and the electrode material, and improve the conductivity of the composite electrolyte, thereby effectively improving the comprehensive electrical performance of the solid-state battery; and the fifth oxide electrolyte has better high-temperature performance, and the high-concentration lithium salt electrolyte has better low-temperature performance, so that the use temperature window of the battery is effectively widened. Specifically, the temperature of the traditional lithium ion battery is in the range of-30 ℃ to 60 ℃; the solid-state battery of the invention can be supported to be used in the range of-40 ℃ to 70 ℃. It should be noted that since the high concentration electrolyte solution contributes to an increase in the interface reaction frequency due to a high density of the ion carrier, a high rate electrode reaction can be realized essentially, and the contrast is more remarkable particularly at low temperatures.
According to still further specific embodiments of the present invention, the mass ratio of the fifth oxide solid-state electrolyte, the polymer electrolyte and the lithium salt is (0 to 1): (0.1-0.5): (0.8-1.2), therefore, the mass ratio of the fifth oxide solid electrolyte, the polymer electrolyte and the lithium salt is limited in the range, the wettability between the fifth oxide electrolyte and the electrode material is further effectively improved, the contact internal resistance of the fifth oxide electrolyte and the electrode material is reduced, the conductivity of the composite electrolyte is improved, and the comprehensive electrical property of the solid-state battery is further effectively improved.
The polymer electrolyte is formed by polymerizing monomers of the polymer electrolyte, and as a specific example, the monomers of the polymer electrolyte include butyl acrylate and glycerol. The specific kind of the above-mentioned fifth oxide electrolyte is not particularly limited, and as some specific examples, the fifth oxide electrolyte may be selected from at least one of garnet-type, perovskite-type, LISICON-type, and NASICON-type solid electrolytes. Also, the specific kind of the above lithium salt is not particularly limited, and as some specific examples, the lithium salt may be selected from at least one of a lithium bis fluorosulfonylimide salt LiFSI, lithium bis (trifluoromethylsulfonyl) imide, and lithium bis (oxalato) borate. Also, the specific kind of the above organic solvent is not particularly limited, and as some specific examples, the organic solvent may be at least one selected from the group consisting of propylene carbonate PC, ethylene carbonate, butylene carbonate, ethylmethyl carbonate, dimethyl carbonate, and diethyl carbonate.
In a second aspect of the invention, a method of making a solid-state battery is presented. According to an embodiment of the invention, the method comprises the steps of:
s100: forming a positive active material layer on a positive current collector
In this step, a positive electrode active material layer is formed on a positive electrode current collector, the positive electrode active material layer including a positive electrode active material, a first conductive agent, a first oxide electrolyte, and a first binder. Preferably, step S100 includes the steps of:
s110: preparation of composite cathode material
In this step, a positive electrode active material, a first conductive agent, a first oxide electrolyte, and a first solvent are mixed, ball-milled, and dried to obtain a composite positive electrode material. Specifically, a first conductive agent (e.g., graphene sheets) is first dispersed in a first solvent (e.g., N-methylpyrrolidone) and uniformly dispersed with ultrasound to obtain a first conductive agent dispersion liquid; then adding the positive electrode active material and the first oxide electrolyte into the first conductive agent dispersion liquid, and effectively compounding the substances in the mixed liquid by adopting a mechanical ball milling mode; and finally, placing the ball-milled mixed product in a vacuum oven for high-temperature (for example, 120 ℃) vacuum-pumping drying for 24-48 hours, effectively volatilizing the solvent, simultaneously well compounding the first conductive agent between the anode material and the oxide electrolyte, and forming a perfect conductive network structure around the anode material particles, thereby improving the comprehensive electrical property of the lithium ion battery on the premise of ensuring the structural stability of the anode active material.
S120: preparation of Positive plate
In this step, the composite positive electrode material, the first binder and the second solvent are mixed to form a positive electrode slurry, and the positive electrode slurry is coated on a positive electrode current collector to form a positive electrode sheet containing a positive electrode active material and an oxide electrolyte material.
S200: forming a positive electrode oxide electrolyte layer on the side of the positive electrode active material layer far away from the positive electrode current collector
In this step, the second oxide electrolyte, the second binder and the solvent (e.g., NMP) are mixed, uniformly dispersed, and then uniformly coated on the side of the positive electrode active material layer away from the positive electrode current collector to form the positive electrode oxide electrolyte layer.
S300: forming a negative active material layer on a negative current collector
In this step, an anode active material layer is formed on the anode current collector, the anode active material layer including an anode active material, a second conductive agent, a fourth oxide electrolyte, and a fourth binder. The step S300 includes the steps of:
s310: preparation of composite cathode Material
In this step, the anode active material, the second conductive agent, the fourth oxide electrolyte, and the third solvent are mixed, ball-milled, and dried to obtain a composite anode material. Specifically, first, a second conductive agent (for example, graphene oxide) is dispersed in a third solvent (for example, deionized water), and the second conductive agent is uniformly dispersed by using ultrasound to obtain a second conductive agent dispersion liquid; then adding the negative electrode active material and the fourth oxide electrolyte into the second conductive agent dispersion liquid, and effectively compounding the substances in the mixed liquid by adopting a mechanical ball milling mode; and finally, placing the ball-milled mixed product in a vacuum oven for high-temperature (for example, 100 ℃) vacuum-pumping drying for 24-48 h, effectively volatilizing the solvent, simultaneously enabling the second conductive agent to be well compounded between the negative electrode material and the oxide electrolyte, and forming a perfect conductive network structure around the negative electrode material particles, so that the comprehensive electrical property of the lithium ion battery is improved on the premise of ensuring the structural stability of the negative electrode active material.
S320: preparation of negative plate
In this step, the composite anode material, the fourth binder and the fourth solvent are mixed to form anode slurry, and the anode slurry is coated on an anode current collector to form an anode sheet containing an anode active material and an oxide electrolyte material.
S400: forming a negative electrode oxide electrolyte layer on the side of the negative electrode active material layer away from the negative electrode current collector
In the step, the third oxide electrolyte, the third binder and the solvent are mixed, uniformly dispersed and then uniformly coated on one side of the negative electrode active material layer far away from the negative electrode current collector to form the negative electrode oxide electrolyte layer.
S500: forming a solid electrolyte layer between the positive electrode oxide electrolyte layer and the negative electrode oxide electrolyte layer
In this step, a solid electrolyte layer is formed between the positive electrode oxide electrolyte layer and the negative electrode oxide electrolyte layer. Preferably, step S500 includes:
s510: the fifth oxide solid electrolyte, a polymer electrolyte monomer, an initiator (e.g., azobisisoheptonitrile ABVN), a lithium salt, and an organic solvent are mixed to obtain a liquid electrolyte.
S520: and injecting the liquid electrolyte into the solid lithium ion battery, heating the battery in a vacuum environment, and carrying out polymerization reaction to obtain a solid electrolyte layer, thereby preparing the solid battery.
According to some embodiments of the present invention, the polymerization temperature is 50 to 80 ℃ and the polymerization time is 2 to 5 hours, thereby ensuring smooth progress of the polymerization.
According to the method of manufacturing a solid-state battery of the embodiment of the present invention, first, the manufactured solid-state battery has no free organic solvent inside, thereby fundamentally solving the safety problem of the battery. And secondly, the conductive agent in the active material layer is compounded between the active material and the oxide electrolyte to form a perfect conductive network structure around the active material particles, so that the comprehensive electrical property of the lithium ion battery is improved on the premise of ensuring the structural stability of the active material. Thirdly, oxide electrolyte layers are respectively prepared on the positive plate and the negative plate by the method, so that the problem of short circuit caused by contact of the positive material and the negative material is solved by replacing a diaphragm, and the conductivity between the active material layer and the solid electrolyte layer is further improved. Fourthly, the polymer electrolyte with good flexibility and the high-conductivity high-concentration lithium salt electrolyte improve the wettability between the fifth oxide electrolyte and the electrode material, reduce the contact internal resistance of the fifth oxide electrolyte and the electrode material, and improve the conductivity of the composite electrolyte, thereby effectively improving the comprehensive electrical property of the solid-state battery; and the fifth oxide electrolyte has better high-temperature performance, and the high-concentration lithium salt electrolyte has better low-temperature performance, so that the use temperature window of the battery is effectively widened.
According to a third aspect of the invention, the invention proposes a vehicle having the above-described solid-state battery or the solid-state battery obtained by the above-described manufacturing method according to an embodiment of the invention. Compared with the prior art, the vehicle safety is higher, the comprehensive electrical property of the battery is more excellent, and the service temperature window of the battery is effectively widened. It should be noted that the features and effects described above for the solid-state battery and the method for manufacturing the solid-state battery are also applicable to the vehicle, and are not described in detail herein.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to one skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
The present embodiment provides a solid-state battery, and a method for manufacturing the solid-state battery includes:
1) A composite positive electrode: firstly, dispersing graphene oxide in N-methyl pyrrolidone, and uniformly dispersing by using ultrasonic to obtain a first conductive agent dispersion liquid; then adding the ternary NCM material and garnet type solid electrolyte into the first conductive agent dispersion liquid, and effectively compounding the substances in the mixed liquid by adopting a mechanical ball milling mode; and finally, placing the ball-milled mixed product in a vacuum oven for vacuum drying at a high temperature of 120 ℃ for 36 hours, effectively volatilizing the solvent, and simultaneously enabling the graphene oxide to be well compounded between the ternary NCM material and the garnet type solid electrolyte to form the composite cathode material. In the step, the mass ratio of the ternary NCM material, the graphene oxide, and the garnet-type solid electrolyte is 100.
And mixing the composite positive electrode material, the binder PVDF and NMP to form positive electrode slurry, and coating the positive electrode slurry on the surface of the positive electrode current collector aluminum foil to prepare the positive electrode plate. In the step, the mass ratio of the composite anode material to the binder is 100:2.5. the thickness of the positive electrode active material layer on the positive electrode sheet was 300 μm.
And mixing the garnet-type solid electrolyte, the binder and NMP, uniformly dispersing, and uniformly coating on one side of the positive active material layer, which is far away from the positive current collector, to form a positive oxide electrolyte layer, thereby obtaining the composite positive electrode. In the step, the mass ratio of the garnet-type solid electrolyte to the binder is 100:2. the thickness of the positive electrode oxide electrolyte layer was 45 μm.
2) And (3) compounding a negative electrode: firstly, dispersing graphene oxide in deionized water, and uniformly dispersing by using ultrasonic to obtain a second conductive agent dispersion liquid; then adding a graphite material and garnet type solid electrolyte into a second conductive agent dispersion liquid, and effectively compounding substances in the mixed liquid by adopting a mechanical ball milling mode; and finally, placing the ball-milled mixed product in a vacuum oven for vacuum drying at a high temperature of 100 ℃ for 36 hours, effectively volatilizing the solvent, and simultaneously enabling the graphene oxide to be well compounded between the negative electrode material and the garnet type solid electrolyte to form the composite negative electrode material. In the step, the mass ratio of the graphite material, the graphene oxide and the garnet-type solid electrolyte is (100).
And mixing the composite negative electrode material, the binder SBR and the deionized water to form negative electrode slurry, and coating the negative electrode slurry on the surface of the copper foil of the negative current collector to prepare the negative electrode sheet. In the step, the mass ratio of the composite negative electrode material to the binder is 100. The thickness of the negative electrode active material layer on the negative electrode sheet was 300 μm.
And mixing the garnet-type solid electrolyte, a binder and a solvent, uniformly dispersing, and then uniformly coating the mixture on one side of the negative active material layer, which is far away from the negative current collector, to form a negative oxide electrolyte layer, thereby obtaining the composite negative electrode. In the step, the mass ratio of the garnet-type solid electrolyte to the binder is 100:2. the thickness of the negative electrode oxide electrolyte layer was 45 μm.
3) Assembling the battery: and winding or laminating the composite positive plates and the composite negative plates at intervals to form a single winding core or a laminated inner core, and filling the single winding core or the laminated inner core into the shell.
4) Injecting a composite electrolyte: the garnet type solid electrolyte, butyl acrylate, a glycerol monomer, an azodiisoheptonitrile initiator and lithium bis (fluorosulfonyl) imide are dissolved in propylene carbonate and injected into the battery, the battery is heated in a vacuum environment, the polymer monomer is subjected to polymerization reaction, and finally the composite solid electrolyte is formed in the battery, so that the solid battery is prepared. In the step, the concentration of the lithium bis (fluorosulfonyl) imide salt in propylene carbonate is 3mol/L, and the mass ratio of the garnet-type solid electrolyte to butyl acrylate to glycerol monomer to the lithium bis (fluorosulfonyl) imide salt to the initiator is 0.5:0.2:0.4:1:0.02.
Example 2
The present embodiment provides a solid-state battery, and a method for manufacturing the solid-state battery includes:
1) A composite positive electrode: firstly, dispersing graphene oxide in N-methyl pyrrolidone, and uniformly dispersing by using ultrasonic to obtain a first conductive agent dispersion liquid; then adding the ternary NCM material and the garnet-type solid electrolyte into the first conductive agent dispersion liquid, and effectively compounding the substances in the mixed liquid by adopting a mechanical ball milling mode; and finally, placing the ball-milled mixed product in a vacuum oven for vacuum drying at a high temperature of 120 ℃ for 36 hours, effectively volatilizing the solvent, and simultaneously enabling the graphene oxide to be well compounded between the ternary NCM material and the garnet type solid electrolyte to form the composite cathode material. In the step, the mass ratio of the ternary NCM material, the graphene oxide, and the garnet-type solid electrolyte is 100.
And mixing the composite positive electrode material, the binder and NMP to form positive electrode slurry, and coating the positive electrode slurry on the surface of the positive electrode current collector aluminum foil to prepare the positive electrode plate. In the step, the mass ratio of the composite positive electrode material to the binder is 100. The thickness of the positive electrode active material layer on the positive electrode sheet was 150 μm.
And mixing the garnet type solid electrolyte, the binder and NMP, uniformly dispersing, and then uniformly coating the mixture on one side of the positive active material layer, which is far away from the positive current collector, to form a positive oxide electrolyte layer, thereby obtaining the composite positive electrode. In this step, the mass ratio of the garnet-type solid electrolyte to the binder was 100. The thickness of the positive electrode oxide electrolyte layer was 10 μm.
2) And (3) compounding a negative electrode: firstly, dispersing graphene oxide in deionized water, and uniformly dispersing by using ultrasonic to obtain a second conductive agent dispersion liquid; then adding a graphite material and garnet type solid electrolyte into a second conductive agent dispersion liquid, and effectively compounding substances in the mixed liquid by adopting a mechanical ball milling mode; and finally, placing the ball-milled mixed product in a vacuum oven for vacuum drying at a high temperature of 100 ℃ for 36 hours, effectively volatilizing the solvent, and simultaneously enabling the graphene oxide to be well compounded between the negative electrode material and the garnet type solid electrolyte to form the composite negative electrode material. In the step, the mass ratio of the graphite material, the graphene oxide and the garnet-type solid electrolyte is 100.
And mixing the composite negative electrode material, the binder SBR and the deionized water to form negative electrode slurry, and coating the negative electrode slurry on the surface of the copper foil of the negative current collector to prepare the negative electrode sheet. In the step, the mass ratio of the composite negative electrode material to the binder is 100:1.5. the thickness of the negative electrode active material layer on the negative electrode sheet was 300 μm.
And mixing the garnet-type solid electrolyte, a binder and a solvent, uniformly dispersing, and then uniformly coating the mixture on one side of the negative active material layer, which is far away from the negative current collector, to form a negative oxide electrolyte layer, thereby obtaining the composite negative electrode. In this step, the mass ratio of the garnet-type solid electrolyte to the binder was 100. The thickness of the negative electrode oxide electrolyte layer was 10 μm.
3) Assembling the battery: and winding or laminating the composite positive plates and the composite negative plates at intervals to form a single winding core or a laminated inner core, and filling the single winding core or the laminated inner core into the shell.
4) Injecting a composite electrolyte: the garnet type solid electrolyte, butyl acrylate, a glycerol monomer, an azodiisoheptonitrile initiator and lithium bis (fluorosulfonyl) imide are dissolved in propylene carbonate and injected into the battery, the battery is heated in a vacuum environment, the polymer monomer is subjected to polymerization reaction, and finally the composite solid electrolyte is formed in the battery, so that the solid battery is prepared. In the step, the concentration of the lithium bis (fluorosulfonyl) imide salt in propylene carbonate is 2.5mol/L, and the mass ratio of the garnet-type solid electrolyte, butyl acrylate, glycerol monomer, lithium bis (fluorosulfonyl) imide salt and initiator is 0.3:0.2:0.4:1:0.02.
example 3
The present embodiment provides a solid-state battery, and a method for manufacturing the solid-state battery includes:
1) A composite positive electrode: firstly, graphene oxide is dispersed in N-methyl pyrrolidone, and the graphene oxide is uniformly dispersed by using ultrasonic waves to obtain a first conductive agent dispersion liquid; then adding the ternary NCM material and garnet type solid electrolyte into the first conductive agent dispersion liquid, and effectively compounding the substances in the mixed liquid by adopting a mechanical ball milling mode; and finally, placing the ball-milled mixed product in a vacuum oven for vacuum drying at a high temperature of 120 ℃ for 36 hours, effectively volatilizing the solvent, and simultaneously enabling the graphene oxide to be well compounded between the ternary NCM material and the garnet type solid electrolyte to form the composite cathode material. In the step, the mass ratio of the ternary NCM material to the graphene oxide to the garnet-type solid electrolyte is 100.
And mixing the composite positive electrode material, the binder SBR and the NMP to form positive electrode slurry, and coating the positive electrode slurry on the surface of the positive electrode current collector aluminum foil to prepare the positive electrode plate. In the step, the mass ratio of the composite positive electrode material to the binder is 100. The thickness of the positive electrode active material layer on the positive electrode sheet was 450 μm.
And mixing the garnet-type solid electrolyte, the binder and NMP, uniformly dispersing, and uniformly coating on one side of the positive active material layer, which is far away from the positive current collector, to form a positive oxide electrolyte layer, thereby obtaining the composite positive electrode. In this step, the mass ratio of the garnet-type solid electrolyte to the binder was 100. The thickness of the positive electrode oxide electrolyte layer was 80 μm.
2) And (3) compounding a negative electrode: firstly, dispersing graphene oxide in deionized water, and uniformly dispersing by using ultrasonic to obtain a second conductive agent dispersion liquid; then adding a graphite material and garnet type solid electrolyte into a second conductive agent dispersion liquid, and effectively compounding substances in the mixed liquid by adopting a mechanical ball milling mode; and finally, placing the ball-milled mixed product in a vacuum oven for vacuum drying at a high temperature of 100 ℃ for 36 hours, effectively volatilizing the solvent, and simultaneously enabling the graphene oxide to be well compounded between the negative electrode material and the garnet type solid electrolyte to form the composite negative electrode material. In the step, the mass ratio of the graphite material, the graphene oxide and the garnet-type solid electrolyte is 100.
And mixing the composite negative electrode material, the binder SBR and the deionized water to form negative electrode slurry, and coating the negative electrode slurry on the surface of the copper foil of the negative current collector to prepare the negative electrode sheet. In the step, the mass ratio of the composite anode material to the binder is 100. The thickness of the negative electrode active material layer on the negative electrode sheet was 300 μm.
And mixing the garnet-type solid electrolyte, a binder and a solvent, uniformly dispersing, and then uniformly coating the mixture on one side of the negative active material layer, which is far away from the negative current collector, to form a negative oxide electrolyte layer, thereby obtaining the composite negative electrode. In this step, the mass ratio of the garnet-type solid electrolyte to the binder was 100. The thickness of the negative electrode oxide electrolyte layer was 80 μm.
3) Assembling the battery: and winding or laminating the composite positive plates and the composite negative plates at intervals to form a single winding core or a laminated inner core, and filling the single winding core or the laminated inner core into the shell.
4) Injecting a composite electrolyte: garnet type solid electrolyte, butyl acrylate, glycerol monomer, azodiisoheptonitrile initiator and lithium bifluorosulfonyl imide are dissolved in propylene carbonate and injected into the battery, the battery is heated in a vacuum environment, the polymer monomer is subjected to polymerization reaction, and finally the composite solid electrolyte is formed in the battery, so that the solid battery is prepared. In the step, the concentration of lithium bis (fluorosulfonyl) imide in propylene carbonate is 4.5mol/L, and the mass ratio of garnet type solid electrolyte, butyl acrylate, glycerol monomer, lithium bis (fluorosulfonyl) imide and initiator is 0.6:0.3:0.6:1:0.02.
example 4
The difference between the embodiment and the embodiment 1 is only that the concentration of the lithium bis (fluorosulfonyl) imide salt in the propylene carbonate is 1mol/L, and the rest is the same as the embodiment 1.
Comparative example 1
The comparative example provides a conventional liquid lithium ion battery, and the preparation method thereof comprises:
1) And (3) positive electrode: and mixing the NCM, the PVDF and the NMP to form anode slurry, and coating the anode slurry on the surface of the aluminum foil of the anode current collector to obtain the anode plate. In this step, the mass ratio of the positive electrode material to the binder was 100. The thickness of the positive electrode active material layer on the positive electrode sheet was 150 μm.
2) Negative electrode: and mixing the negative electrode material graphite, the binder SBR and the deionized water to form negative electrode slurry, and coating the negative electrode slurry on the surface of the negative current collector copper foil to prepare the negative electrode sheet. In the step, the mass ratio of the negative electrode material to the binder is 100. The thickness of the negative electrode active material layer on the negative electrode sheet was 300 μm.
3) Assembling the battery: and winding or laminating the positive plates and the negative plates alternately to form a single winding core or a laminated inner core, and filling the single winding core or the laminated inner core into the shell.
4) Injecting liquid electrolyte: the traditional liquid electrolyte comprises 1mol/L lithium hexafluorophosphate, EC/EMC/DMC (mass ratio of 1.
Comparative example 2
The present embodiment provides a solid-state battery, and a method for manufacturing the solid-state battery includes:
1) A composite positive electrode: adding a ternary NCM material and garnet type solid electrolyte into N-methyl pyrrolidone, and effectively compounding by adopting a mechanical ball milling mode; and finally, placing the mixed product after ball milling in a vacuum oven for vacuum drying for 36 hours at a high temperature of 120 ℃, and effectively volatilizing the solvent to form the composite anode material. In this step, the mass ratio of the ternary NCM material to the garnet-type solid electrolyte is 100.
And mixing the composite positive electrode material, the binder and NMP to form positive electrode slurry, and coating the positive electrode slurry on the surface of the positive electrode current collector aluminum foil to prepare the positive electrode plate. In the step, the mass ratio of the composite cathode material to the binder is 100. The thickness of the positive electrode active material layer on the positive electrode sheet was 150 μm.
And mixing the garnet-type solid electrolyte, the binder and NMP, uniformly dispersing, and uniformly coating on one side of the positive active material layer, which is far away from the positive current collector, to form a positive oxide electrolyte layer, thereby obtaining the composite positive electrode. In this step, the mass ratio of the garnet-type solid electrolyte to the binder was 100. The thickness of the positive electrode oxide electrolyte layer was 10 μm.
2) And (3) compounding a negative electrode: adding a graphite material and garnet type solid electrolyte into deionized water, and effectively compounding substances in the mixed solution by adopting a mechanical ball milling mode; and finally, placing the mixed product after ball milling in a vacuum oven for vacuum drying for 36 hours at a high temperature of 100 ℃, and effectively volatilizing the solvent to form the composite cathode material. In this step, the mass ratio of the graphite material to the garnet-type solid electrolyte was 100.
And mixing the composite negative electrode material, the binder SBR and the deionized water to form negative electrode slurry, and coating the negative electrode slurry on the surface of the copper foil of the negative current collector to prepare the negative electrode sheet. In the step, the mass ratio of the composite negative electrode material to the binder is 100:1.5. the thickness of the negative electrode active material layer on the negative electrode sheet was 300 μm.
And mixing the garnet-type solid electrolyte, a binder and a solvent, uniformly dispersing, and then uniformly coating the mixture on one side of the negative active material layer, which is far away from the negative current collector, to form a negative oxide electrolyte layer, thereby obtaining the composite negative electrode. In this step, the mass ratio of the garnet-type solid electrolyte to the binder was 100. The thickness of the negative electrode oxide electrolyte layer was 10 μm.
3) Assembling the battery: and (3) winding or laminating the composite positive plates and the composite negative plates at intervals to form a single winding core or a laminated inner core, and filling the winding core or the laminated inner core into the shell to obtain the solid-state battery.
The batteries prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to low-temperature discharge, high-temperature cycle and safety performance tests, and the test results are shown in table 1, and it can be seen from the test results that the safety performance of the batteries in examples 1 to 4 and comparative example 2 was acceptable in all the solid-state batteries, the safety performance of the conventional liquid-state lithium ion battery in comparative example 1 did not pass the safety performance test, and the high-temperature cycle efficiency of the batteries in examples 1 to 4 and comparative example 2 was superior to that of comparative example 1. The comparative example 1 has good low-temperature discharge performance, while the comparative example 2 only adopts oxide solid electrolyte to greatly reduce the low-temperature performance; examples 1 to 3 significantly improved low temperature performance using the composite solid electrolyte and the high concentration electrolyte, and example 4 had limited improvement in low temperature performance using the composite solid electrolyte and the low concentration electrolyte. As can be seen, examples 1-3 not only passed the safety performance test, but also both the low temperature performance and the high temperature performance were excellent.
TABLE 1
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A solid-state battery, comprising:
the positive plate comprises a positive current collector and a positive active material layer formed on the positive current collector, wherein the positive active material layer comprises a positive active material, a first conductive agent, a first oxide electrolyte and a first binder;
a positive electrode oxide electrolyte layer disposed on a side of the positive electrode active material layer away from the positive electrode current collector, the positive electrode oxide electrolyte layer including a second oxide electrolyte and a second binder;
the solid electrolyte layer is arranged on one side of the positive electrode oxide electrolyte layer far away from the positive electrode sheet;
the negative oxide electrolyte layer is arranged on one side of the solid electrolyte layer far away from the positive oxide electrolyte layer and comprises a third oxide electrolyte and a third binder;
the negative pole piece, the negative pole piece includes negative pole mass flow body and negative active material layer, the negative active material layer sets up keeping away from on negative oxide electrolyte layer one side on solid state electrolyte layer, the negative pole mass flow body sets up keeping away from on the negative active material layer one side on negative oxide electrolyte layer, the negative active material layer includes negative active material, second conductive agent, fourth oxide electrolyte and fourth binder.
2. The solid-state battery according to claim 1, wherein the mass ratio of the positive electrode active material, the first conductive agent, and the first oxide electrolyte is 100 (0.1-10) to (3-20);
optionally, the thickness of the positive electrode active material layer is 150 to 450 μm.
3. The solid-state battery according to claim 1, wherein a mass ratio of the second oxide electrolyte to the second binder is 100 (0.1 to 5);
optionally, the thickness of the positive electrode oxide electrolyte layer is 10 to 80 μm.
4. The solid-state battery according to claim 1, wherein the solid-state electrolyte layer comprises a fifth oxide solid-state electrolyte, a polymer electrolyte, a lithium salt, and an organic solvent, wherein the concentration of the lithium salt in the organic solvent is 2.5 to 4.5mol/L, preferably 3 to 4mol/L;
optionally, the mass ratio of the fifth oxide solid electrolyte, the polymer electrolyte and the lithium salt is (0-1): (0.1-0.5): (0.8-1.2);
optionally, the fifth oxide electrolyte is selected from at least one of garnet-type solid electrolytes, perovskite-type solid electrolytes, LISICON-type solid electrolytes, and NASICON-type solid electrolytes;
optionally, the monomers of the polymer electrolyte include butyl acrylate and glycerol;
optionally, the lithium salt is selected from at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, and lithium bis (oxalato) borate;
optionally, the organic solvent is selected from at least one of propylene carbonate, ethylene carbonate, butylene carbonate, ethylmethyl carbonate, dimethyl carbonate, and diethyl carbonate.
5. The solid-state battery according to claim 1, wherein the mass ratio of the negative electrode active material, the second conductive agent, and the fourth oxide electrolyte is 100 (0.1-10) to (3-20);
optionally, the thickness of the negative active material layer is 200 to 500 μm;
optionally, the mass ratio of the third oxide electrolyte to the third binder is 100 (0.1-5);
optionally, the thickness of the anode oxide electrolyte layer is 10 to 80 μm.
6. The solid-state battery according to claim 1, wherein the positive electrode active material is selected from at least one of a ternary NCM material and an LFP material;
optionally, the first oxide electrolyte, the second oxide electrolyte, the third oxide electrolyte, and the fourth oxide electrolyte are each independently selected from at least one of a garnet-type solid electrolyte, a perovskite-type solid electrolyte, a LISICON-type solid electrolyte, and a NASICON-type solid electrolyte;
optionally, the first conductive agent and the second conductive agent are each independently selected from at least one of graphene and graphene oxide;
optionally, the negative active material is selected from at least one of a graphite material, hard carbon, soft carbon, a silicon material, and a silicon-carbon composite material.
7. A method of producing the solid-state battery according to any one of claims 1 to 6, comprising:
(1) Forming a positive electrode active material layer on a positive electrode current collector, the positive electrode active material layer including a positive electrode active material, a first conductive agent, a first oxide electrolyte, and a first binder;
(2) Forming a positive electrode oxide electrolyte layer on one side of the positive electrode active material layer far away from the positive electrode current collector, wherein the positive electrode oxide electrolyte layer comprises a second oxide electrolyte and a second binder;
(3) Forming a negative electrode active material layer on the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a second conductive agent, a fourth oxide electrolyte, and a fourth binder;
(4) Forming a negative electrode oxide electrolyte layer on one side of the negative electrode active material layer far away from the negative electrode current collector, wherein the negative electrode oxide electrolyte layer comprises a third oxide electrolyte and a third binder;
(5) A solid electrolyte layer is formed between the positive electrode oxide electrolyte layer and the negative electrode oxide electrolyte layer.
8. The method of claim 7, wherein step (1) comprises:
(1-1) mixing a positive electrode active material, a first conductive agent, a first oxide electrolyte and a first solvent, ball-milling, and drying to obtain a composite positive electrode material;
(1-2) mixing the composite positive electrode material, the first binder and the second solvent to form positive electrode slurry, and coating the positive electrode slurry on a positive electrode current collector to form a positive electrode plate.
9. The method of claim 7, wherein step (3) comprises:
(3-1) mixing the negative electrode active material, the second conductive agent, the fourth oxide electrolyte and the third solvent, ball-milling and drying to obtain a composite negative electrode material;
(3-2) mixing the composite negative electrode material, a fourth binder and a fourth solvent to form negative electrode slurry, and coating the negative electrode slurry on a negative electrode current collector to form a negative electrode sheet;
optionally, step (5) comprises:
(5-1) mixing the fifth oxide solid electrolyte, a polymer electrolyte monomer, an initiator, a lithium salt and an organic solvent to obtain a liquid electrolyte;
(5-2) injecting the liquid electrolyte into a solid lithium ion battery to perform polymerization reaction so as to obtain a solid electrolyte layer;
optionally, the temperature of the polymerization reaction is 50-80 ℃, and the time of the polymerization reaction is 2-5 hours.
10. A vehicle comprising the solid-state battery according to any one of claims 1 to 6 or a solid-state battery produced by the method according to any one of claims 7 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118040074A (en) * | 2024-04-11 | 2024-05-14 | 蜂巢能源科技股份有限公司 | Semi-solid lithium ion battery and preparation method thereof |
| CN118522979A (en) * | 2024-07-23 | 2024-08-20 | 瑞浦兰钧能源股份有限公司 | Positive electrode plate, solid-state battery containing positive electrode plate and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118040074A (en) * | 2024-04-11 | 2024-05-14 | 蜂巢能源科技股份有限公司 | Semi-solid lithium ion battery and preparation method thereof |
| CN118522979A (en) * | 2024-07-23 | 2024-08-20 | 瑞浦兰钧能源股份有限公司 | Positive electrode plate, solid-state battery containing positive electrode plate and preparation method |
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