CN112582666A - Bipolar lithium ion battery and preparation method thereof - Google Patents
Bipolar lithium ion battery and preparation method thereof Download PDFInfo
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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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
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the technical field of lithium batteries, and relates to a bipolar lithium ion battery and a preparation method thereof. The bipolar lithium ion battery includes: a first bipolar current collector and at least one battery cell; each of the battery cells includes: a composite positive electrode, a solid electrolyte membrane, a composite negative electrode or a metallic lithium foil negative electrode, and a second bipolar current collector; the first bipolar current collector, the composite positive electrode in each battery cell, the solid electrolyte membrane, the composite negative electrode or the metallic lithium foil negative electrode, and the second bipolar current collector are sequentially stacked; the solid electrolyte membrane is prepared by mixing a first solid electrolyte and a first organic solvent, coating the mixture on a first substrate, drying and peeling; the first solid electrolyte includes: a polymer solid electrolyte or a mixture of a polymer solid electrolyte and an oxide solid electrolyte. The bipolar lithium ion battery can avoid the short circuit between the anode and the cathode of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a bipolar lithium ion battery and a preparation method thereof.
Background
Among the numerous energy storage devices, lithium ion batteries are of interest due to their high energy and power densities. However, the lithium ion battery widely used at present and adopting flammable and volatile organic liquid electrolyte as an ion conducting medium has great potential safety hazard. The all-solid-state battery uses solid electrolyte to replace flammable and volatile organic liquid electrolyte as an ion conduction medium, can fundamentally solve the safety problem of the lithium ion battery, and has higher energy density and longer cycle life.
When lithium ion batteries are used as power sources for various automobiles, a plurality of unit batteries need to be connected in series to ensure a high power output. However, when the unit cells are externally connected, the output capacity of the battery is reduced due to large impedance caused by small area of the connection portion, and the volume and weight of the battery pack are increased by connecting a plurality of unit cells in series, and the energy density and the power density of the battery are accordingly reduced. One of the methods for solving this problem is to prepare a bipolar battery and to realize internal series connection of the batteries. The solid electrolyte has no fluidity, and can effectively avoid short circuit between the positive electrode and the negative electrode in the bipolar battery.
At present, most of bipolar batteries are assembled by using a gel electrolyte, and the gel electrolyte contains a certain amount of liquid components, so that short circuit caused by connection of positive and negative electrodes in the battery through the liquid components cannot be completely avoided in practical application.
Disclosure of Invention
The invention aims to provide an all-solid-state bipolar lithium ion battery to avoid short circuit of the bipolar lithium ion battery.
In order to achieve the above object, the present invention provides a bipolar lithium ion battery. The bipolar lithium ion battery includes: a first bipolar current collector and at least one battery cell;
each of the battery cells includes: a composite positive electrode, a solid electrolyte membrane, a composite negative electrode or a metallic lithium foil negative electrode, and a second bipolar current collector;
the first bipolar current collector, the composite positive electrode in each battery cell, the solid electrolyte membrane, the composite negative electrode or the metallic lithium foil negative electrode, and the second bipolar current collector are sequentially stacked;
the solid electrolyte membrane is prepared by mixing a first solid electrolyte and a first organic solvent, coating the mixture on a first substrate, drying and peeling;
the first solid electrolyte includes: a polymer solid electrolyte or a mixture of a polymer solid electrolyte and an oxide solid electrolyte.
Specifically, the drying temperature is 20 ℃ to 100 ℃.
Specifically, the mass fraction of the oxide solid electrolyte in the first solid electrolyte is 0-80%, preferably 5-60%, such as 5%, 10%, 20% or 50%.
Specifically, the polymer solid electrolyte is a mixture of a polymer matrix and a lithium salt;
wherein the polymer matrix comprises: at least one of polyethylene oxide (PEO), polypropylene oxide (PPO), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), and Polyacrylonitrile (PAN);
the lithium salt includes: LiN (SO)2CF3)2、LiClO4、LiSO2CF3、LiB(C2O4)2、LiPF6And LiI.
More specifically, the mass fraction of the lithium salt in the polymer solid electrolyte is 10% to 50%.
Specifically, the oxide solid electrolyte includes: at least one of Lithium Lanthanum Zirconium Oxide (LLZO), tantalum-doped lithium lanthanum zirconium oxide (LLZTO), gallium-doped lithium lanthanum zirconium oxide (Ga-LLZO), Lithium Lanthanum Titanium Oxide (LLTO), titanium aluminum lithium phosphate (LATP), and germanium aluminum lithium phosphate (LAGP).
Specifically, the first substrate is a glass substrate, a metal substrate or a polytetrafluoroethylene substrate.
Specifically, the first organic solvent includes: at least one of acetonitrile, acetone, tetrahydrofuran, Dimethylformamide (DMF), Dimethylacetamide (DMAC), Tetramethylurea (TMU), Dimethylsulfoxide (DMSO), triethylphosphate, N-methyl-2-pyrrolidone (NMP).
Specifically, the composite positive electrode is prepared by a method comprising the following steps:
mixing a second solid electrolyte, a positive electrode active material, a first electronic conductive additive and a second organic solvent to prepare a first slurry;
and coating the first slurry on a second substrate, and peeling the second substrate after drying to prepare the composite positive electrode.
More specifically, the mass fractions of the second solid electrolyte, the positive electrode active material, and the first electron conductive additive in the first slurry are 10% to 30%, 60% to 80%, and 5% to 10%, such as 25% to 30%, 65% to 70%, and 5% to 8%, respectively.
More specifically, the second solid electrolyte includes: a polymer solid electrolyte or a mixture of a polymer solid electrolyte and an oxide solid electrolyte.
More specifically, the mass fraction of the oxide solid electrolyte in the second solid electrolyte is 0 to 80%, preferably 5% to 80%, such as 5%, 10%, 50% or 80%.
More specifically, in the second solid electrolyte, the polymer solid electrolyte is a mixture of a polymer matrix and a lithium salt;
wherein, in the second solid-state electrolyte, the polymer matrix comprises: at least one of polyethylene oxide, polypropylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, and polyacrylonitrile;
in the second solid electrolyte, the lithium salt includes: LiN (SO)2CF3)2、LiClO4、LiSO2CF3、LiB(C2O4)2、LiPF6And LiI.
Specifically, in the second solid electrolyte, the mass fraction of the lithium salt in the polymer solid electrolyte is 10% to 50%.
Specifically, in the second solid electrolyte, the oxide solid electrolyte includes: at least one of Lithium Lanthanum Zirconium Oxide (LLZO), tantalum-doped lithium lanthanum zirconium oxide (LLZTO), gallium-doped lithium lanthanum zirconium oxide (Ga-LLZO), Lithium Lanthanum Titanium Oxide (LLTO), titanium aluminum lithium phosphate (LATP), and germanium aluminum lithium phosphate (LAGP).
More specifically, the positive electrode active material includes: lithium cobaltate, lithium manganate, nickel cobalt manganese ternary, lithium iron phosphate and lithium nickel manganese.
More specifically, the first electronically conductive additive comprises: at least one of carbon black, carbon nanotubes, graphene, and carbon fibers.
More specifically, the second substrate is a metal foil, such as an aluminum foil or a copper foil.
More specifically, the second organic solvent includes: at least one of acetonitrile, acetone, tetrahydrofuran, Dimethylformamide (DMF), Dimethylacetamide (DMAC), Tetramethylurea (TMU), Dimethylsulfoxide (DMSO), triethylphosphate, N-methyl-2-pyrrolidone (NMP).
Specifically, the composite negative electrode is prepared by the following steps:
mixing a third solid electrolyte, a negative electrode active material, a second electronic conductive additive and a third organic solvent to prepare a second slurry;
and coating the second slurry on a third substrate, and peeling the third substrate after drying to prepare the composite negative electrode.
More specifically, the mass fractions of the third solid electrolyte, the negative electrode active material, and the second electron conductive additive in the second slurry are 10% to 35%, 60% to 80%, and 5% to 10%, for example, 20% to 30%, 65% to 75%, and 5% to 8%, respectively.
More specifically, the third solid electrolyte includes: a polymer solid electrolyte or a mixture of a polymer solid electrolyte and an oxide solid electrolyte.
More specifically, the mass fraction of the oxide solid electrolyte in the third solid electrolyte is 0 to 80%, preferably 5% to 50%, such as 5%, 8%, 10% or 15%.
In the third solid electrolyte, the polymer solid electrolyte is a mixture of a polymer matrix and a lithium salt;
wherein, in the third solid-state electrolyte, the polymer matrix comprises: at least one of polyethylene oxide, polypropylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, and polyacrylonitrile;
in the third solid electrolyte, the lithium salt includes: LiN (SO)2CF3)2、LiClO4、LiSO2CF3、LiB(C2O4)2、LiPF6And LiI.
Specifically, in the third solid electrolyte, the mass fraction of the lithium salt in the polymer solid electrolyte is 10% to 50%.
Specifically, in the third solid-state electrolyte, the oxide solid-state electrolyte includes: at least one of Lithium Lanthanum Zirconium Oxide (LLZO), tantalum-doped lithium lanthanum zirconium oxide (LLZTO), gallium-doped lithium lanthanum zirconium oxide (Ga-LLZO), Lithium Lanthanum Titanium Oxide (LLTO), titanium aluminum lithium phosphate (LATP), and germanium aluminum lithium phosphate (LAGP).
More specifically, the anode active material includes: at least one of graphite, amorphous carbon, mesocarbon microbeads, nano-silicon, silicon carbon material and lithium titanate.
More specifically, the third solid electrolyte includes: a polymer solid electrolyte or a mixture of a polymer solid electrolyte and an oxide solid electrolyte.
More specifically, the second electronically conductive additive comprises: at least one of carbon black, carbon nanotubes, graphene, and carbon fibers.
More specifically, the third substrate is a metal foil, such as an aluminum foil or a copper foil.
More specifically, the third organic solvent includes: at least one of acetonitrile, acetone, tetrahydrofuran, Dimethylformamide (DMF), Dimethylacetamide (DMAC), Tetramethylurea (TMU), Dimethylsulfoxide (DMSO), triethylphosphate, N-methyl-2-pyrrolidone (NMP).
Specifically, the thickness of the lithium metal foil negative electrode is 5 to 100 μm, for example, 50 μm.
Specifically, the first bipolar current collector is a copper foil with an aluminum coating on one side or an aluminum foil with a copper coating on one side.
More specifically, the aluminum coating is deposited on the copper foil by a Physical Vapor Deposition (PVD) method or a Chemical Vapor Deposition (CVD) method.
Specifically, the second bipolar current collector is a copper foil with an aluminum coating on one side or an aluminum foil with a copper coating on one side.
More specifically, the copper coating is deposited on the aluminum foil by a Physical Vapor Deposition (PVD) method or a Chemical Vapor Deposition (CVD) method.
Specifically, the number of the battery cells is two or more, for example, 4 or 6 battery cells.
The invention also provides a preparation method of the bipolar lithium ion battery. The method comprises the following steps:
and sequentially laminating the first bipolar current collector, the composite positive electrode in each battery unit, the solid electrolyte membrane, the composite negative electrode or the metal lithium foil negative electrode and the second bipolar current collector, and then packaging to obtain the bipolar lithium ion battery.
Specifically, the method further comprises connecting each composite positive electrode in the bipolar lithium ion battery with an aluminum coating or an aluminum foil of the first bipolar current collector or the second bipolar current collector, and connecting each composite negative electrode or a metal lithium foil negative electrode with a copper foil or a copper coating of the second bipolar current collector.
The bipolar lithium ion battery provided by the invention takes the solid electrolyte membrane as the ion transport carrier, is a bipolar all-solid-state lithium ion battery, and avoids the short circuit between the anode and the cathode of the battery compared with the existing bipolar lithium ion battery which takes the electrolyte as the ion transport carrier. In addition, for the existing bipolar lithium ion battery, the bipolar lithium ion battery provided by the invention has the advantages of small volume and light weight, relatively improves the single voltage and energy density of the battery, and has good electrochemical performance.
The anode and the cathode in the bipolar lithium ion battery provided by the invention are both composite electrodes independently formed into films, so that the coating on the bipolar current collector can be prevented from being damaged in the electrode coating process.
The bipolar current collector in the bipolar lithium ion battery provided by the invention is a copper foil with an aluminum coating on the surface or an aluminum foil with a copper coating on the surface, so that the conductivity of the bipolar lithium ion battery is improved, and the manufacturing cost of the bipolar lithium ion battery is reduced.
The bipolar lithium ion battery provided by the invention can regulate and control the voltage of the battery by adjusting the number of the battery units connected in series.
The preparation method of the bipolar lithium ion battery provided by the invention is simple and convenient to manufacture by a simple lamination packaging process.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a schematic diagram of a bipolar lithium ion battery provided by the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Example 1
(1) Mixing PVDF polymer solid electrolyte, nickel-cobalt-manganese ternary material and carbon black according to the proportion of 20: 75: 5 and NMP solvent, coating the mixture on an aluminum foil, drying the aluminum foil for 2 hours at 110 ℃, and stripping the aluminum foil after drying to obtain the composite positive pole piece independently formed into a film.
(2) Mixing a solid electrolyte composed of a PVDF polymer solid electrolyte and a LLZTO solid electrolyte mixture, graphite and carbon nano tubes according to the weight ratio of 20: 75: 5 and a DMF solvent are mixed according to a mass ratio to prepare slurry, the slurry is coated on a copper foil, the copper foil is dried for 6 hours at the temperature of 80 ℃, and the dried copper foil is stripped to obtain the composite negative pole piece independently formed into a film.
(3) Mixing PVDF polymer electrolyte, LLZTO solid electrolyte and DMF, coating on a glass substrate, drying to obtain a composite solid electrolyte membrane, wherein the oxide electrolyte accounts for 10% of the solid electrolyte (total mass of polymer electrolyte and oxide electrolyte), the drying temperature is 30 deg.C, and automatically peeling to obtain the solid electrolyte membrane.
(4) And stacking a first bipolar current collector, a composite positive electrode, a solid electrolyte membrane, a composite negative electrode and a second bipolar current collector in sequence, and connecting 4 layers of battery units in series inside, wherein the first bipolar current collector and the second bipolar current collector are both Cu foils with Al metal layers sputtered on one sides, and the positive electrode is arranged on one side of Al and the negative electrode is arranged on one side of Cu when the battery is assembled.
(5) And packaging the lamination to obtain the bipolar lithium ion battery.
Example 2
(1) Mixing a solid electrolyte composed of a mixture of a PVDF polymer solid electrolyte and a LLTO solid electrolyte, a nickel-cobalt-manganese ternary material and graphene according to the weight ratio of 30: 60: 10 and DMAC solvent to prepare slurry, coating the slurry on an aluminum foil, drying the aluminum foil for 2 hours at 110 ℃, and stripping the dried aluminum foil to obtain the composite positive pole piece independently formed into a film.
(2) Mixing PEO polymer solid electrolyte, a silicon-carbon negative electrode and carbon black according to the weight ratio of 20: 75: 5 and a tetrahydrofuran solvent, coating the slurry on a copper foil, drying for 10 hours at 50 ℃, and stripping from the copper foil after drying to obtain the composite negative pole piece independently formed into a film.
(3) The PVDF polymer electrolyte, Ga-doped LLZTO solid electrolyte and NMP are mixed, coated on a glass substrate, and dried to obtain the composite solid electrolyte membrane, wherein the oxide electrolyte accounts for 20% of the solid electrolyte (the total mass of the polymer electrolyte and the oxide electrolyte), and the composite solid electrolyte membrane is automatically stripped at the drying temperature of 50 ℃ to obtain the solid electrolyte membrane.
(4) And stacking a first bipolar current collector, a composite positive electrode, a solid electrolyte membrane, a composite negative electrode and a second bipolar current collector in sequence, and connecting 2 layers of battery units in series inside, wherein the first bipolar current collector and the second bipolar current collector are both Cu foils with Al metal layers sputtered on one sides, and the positive electrode is arranged on one side of Al and the negative electrode is arranged on one side of Cu when the battery is assembled.
(5) And packaging the lamination to obtain the bipolar lithium ion battery.
Example 3
(1) Mixing PVDF-HFP polymer solid electrolyte, lithium manganate and carbon black according to the weight ratio of 10: 80: 10 and DMF solvent, coating the mixture on an aluminum foil, drying the aluminum foil for 4 hours at 100 ℃, and stripping the aluminum foil after drying to obtain the composite positive pole piece independently formed into a film.
(2) A lithium metal foil was used for the negative electrode, and the thickness was 50 μm.
(3) PVDF-HFP polymer electrolyte, LATP solid electrolyte and DMAC are mixed and coated on a polytetrafluoroethylene substrate, and the mixture is dried to obtain a composite solid electrolyte membrane, wherein the oxide electrolyte accounts for 50% of the solid electrolyte (the total mass of the polymer electrolyte and the oxide electrolyte), the drying temperature is 80 ℃, and the composite solid electrolyte membrane is obtained by automatic stripping.
(4) And stacking a first bipolar current collector, a composite positive electrode, a solid electrolyte membrane, a metal lithium foil negative electrode and a second bipolar current collector in sequence, and connecting 5 layers of battery units in series inside, wherein the first bipolar current collector and the second bipolar current collector are both Cu foils with Al metal layers plated on one sides, and the positive electrode is arranged on one side of Al and the negative electrode is arranged on one side of Cu when the battery is assembled.
And finally, packaging the lamination to obtain the bipolar lithium ion battery.
Example 4
(1) Mixing PAN polymer solid electrolyte, lithium cobaltate material and carbon black according to the weight ratio of 10: 80: 10 and NMP solvent, coating the mixture on an aluminum foil, drying the aluminum foil for 6 hours at 90 ℃, and stripping the aluminum foil after drying to obtain the composite positive pole piece 1 with an independent film.
(2) Mixing PEO polymer solid electrolyte, lithium titanate and carbon nano tubes according to the weight ratio of 25: 65: 10 and an acetone solvent, coating the mixture on a copper foil, drying the copper foil for 6 hours at 50 ℃, and stripping the dried copper foil to obtain the composite negative pole piece 3 independently formed into a film.
(3) PAN polymer electrolyte, LLTO solid electrolyte and DMAC are mixed and coated on a polytetrafluoroethylene substrate, and the mixture is dried to obtain the composite solid electrolyte membrane, wherein the oxide electrolyte accounts for 70% of the solid electrolyte (the total mass of the polymer electrolyte and the oxide electrolyte), the drying temperature is 100 ℃, and the composite solid electrolyte membrane 2 is obtained by automatic stripping.
(4) And (3) laminating a first bipolar current collector 6, a composite positive electrode 1, a solid electrolyte membrane 2, a composite negative electrode 3 and a second bipolar current collector 4 in sequence, and connecting 6 layers of battery units 5 in series inside, wherein the first bipolar current collector 6 and the second bipolar current collector 4 are both Al foils with Cu metal layers sputtered on one sides, and the positive electrode is arranged on one side of Al and the negative electrode is arranged on one side of Cu when the battery is assembled.
(5) The packaging stack yields a bipolar lithium ion battery as shown in fig. 1.
Example 5
(1) PEO polymer solid electrolyte, lithium iron phosphate and carbon black are mixed according to the weight ratio of 20: 75: 5 and acetonitrile solvent, coating the mixture on an aluminum foil, drying the aluminum foil for 12 hours at 50 ℃, and stripping the aluminum foil after drying to obtain the composite positive pole piece independently formed into a film.
(2) A lithium metal foil was used for the negative electrode, and the thickness was 50 μm.
(3) The PEO polymer electrolyte, the LLZO solid electrolyte and acetonitrile are mixed, coated on a polytetrafluoroethylene substrate and dried to obtain the composite solid electrolyte membrane, wherein the oxide electrolyte accounts for 60 percent of the solid electrolyte (the total mass of the polymer electrolyte and the oxide electrolyte), the drying temperature is 30 ℃, and the solid electrolyte membrane is obtained by automatic stripping.
(4) And stacking a first bipolar current collector, a composite positive electrode, a solid electrolyte membrane, a metal lithium foil negative electrode and a second bipolar current collector in sequence, and connecting 3 layers of battery units in series inside, wherein the first bipolar current collector and the second bipolar current collector are both Cu foils with Al metal layers plated on one sides, and the positive electrode is arranged on one side of Al and the negative electrode is arranged on one side of Cu when the battery is assembled.
(5) And packaging the lamination to obtain the bipolar lithium ion battery.
Example 6
Performance measurements were performed on the bipolar lithium ion batteries prepared in examples 1 to 5.
TABLE 1 Primary discharge Capacity of Bipolar lithium ion batteries prepared in examples 1-5
According to the embodiment, the bipolar lithium ion battery has excellent electrochemical performance, the voltage of the single battery can be increased or decreased by controlling the increase and decrease of the number of the series battery units, the use of external series components of the battery in the PACK process can be reduced, and the energy density of the system is further improved.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A bipolar lithium ion battery, comprising: a first bipolar current collector and at least one battery cell;
each of the battery cells includes: a composite positive electrode, a solid electrolyte membrane, a composite negative electrode or a metallic lithium foil negative electrode, and a second bipolar current collector;
the first bipolar current collector, the composite positive electrode in each battery cell, the solid electrolyte membrane, the composite negative electrode or the metallic lithium foil negative electrode, and the second bipolar current collector are sequentially stacked;
the solid electrolyte membrane is prepared by mixing a first solid electrolyte and a first organic solvent, coating the mixture on a first substrate, drying and peeling;
the first solid electrolyte includes: a polymer solid electrolyte or a mixture of a polymer solid electrolyte and an oxide solid electrolyte.
2. The bipolar lithium ion battery of claim 1, wherein the mass fraction of the oxide solid electrolyte in the first solid electrolyte is 0-80%.
3. The bipolar lithium ion battery of claim 1, wherein the polymer solid electrolyte is a mixture of a polymer matrix and a lithium salt;
wherein the polymer matrix comprises: at least one of polyethylene oxide, polypropylene oxide, polyvinylidene fluoride-hexafluoropropylene copolymer, and polyacrylonitrile;
the lithium salt includes: LiN (SO)2CF3)2、LiClO4、LiSO2CF3、LiB(C2O4)2、LiPF6And LiI;
preferably, the mass fraction of the lithium salt in the polymer solid electrolyte is 10% to 50%.
4. The bipolar lithium ion battery of claim 1, wherein the oxide solid state electrolyte comprises: at least one of lithium lanthanum zirconium oxygen, tantalum-doped lithium lanthanum zirconium oxygen, gallium-doped lithium lanthanum zirconium oxygen, lithium lanthanum titanium oxygen, lithium titanium aluminum phosphate, and lithium germanium aluminum phosphate.
5. The bipolar lithium ion battery of claim 1, wherein the first organic solvent comprises: at least one of acetonitrile, acetone, tetrahydrofuran, dimethylformamide, dimethylacetamide, tetramethylurea, dimethyl sulfoxide, triethyl phosphate, and N-methyl-2-pyrrolidone;
preferably, the first substrate is a glass substrate, a metal substrate, or a teflon substrate.
6. The bipolar lithium ion battery of claim 1, wherein the composite positive electrode is made by a method comprising:
mixing a second solid electrolyte, a positive electrode active material, a first electronic conductive additive and a second organic solvent to prepare a first slurry;
coating the first slurry on a second substrate, and peeling the second substrate after drying to prepare the composite positive electrode;
the composite negative electrode is prepared by a method comprising the following steps:
mixing a third solid electrolyte, a negative electrode active material, a second electronic conductive additive and a third organic solvent to prepare a second slurry;
and coating the second slurry on a third substrate, and peeling the third substrate after drying to prepare the composite negative electrode.
7. The bipolar lithium ion battery of claim 6, wherein the mass fractions of the second solid electrolyte, the positive electrode active material, and the first electron conductive additive in the first slurry are 10% to 30%, 60% to 80%, and 5% to 10%, respectively;
the third solid electrolyte, the negative electrode active material and the second electronic conductive additive are respectively 10-35%, 60-80% and 5-10% in mass fraction in the second slurry.
8. The bipolar lithium ion battery of claim 6, wherein the positive active material comprises: at least one of lithium cobaltate, lithium manganate, nickel cobalt manganese ternary, lithium iron phosphate and lithium nickel manganese;
the negative active material includes: at least one of graphite, amorphous carbon, mesocarbon microbeads, nano-silicon, silicon carbon material and lithium titanate;
preferably, the second solid-state electrolyte and the third solid-state electrolyte each include: a polymer solid electrolyte or a mixture of a polymer solid electrolyte and an oxide solid electrolyte;
preferably, the first and second electronically conductive additives each comprise: at least one of carbon black, carbon nanotubes, graphene, and carbon fibers;
preferably, the second substrate and the third substrate are both aluminum foil or copper foil.
9. The bipolar lithium ion battery of claim 1, wherein the first bipolar current collector is a copper foil with an aluminum coating on one side or an aluminum foil with a copper coating on one side;
the second bipolar current collector is a copper foil with an aluminum coating on one side or an aluminum foil with a copper coating on one side.
10. The method for preparing a bipolar lithium ion battery according to any one of claims 1 to 9, wherein the method comprises the following steps:
and sequentially laminating the first bipolar current collector, the composite positive electrode in each battery unit, the solid electrolyte membrane, the composite negative electrode or the metal lithium foil negative electrode and the second bipolar current collector, and then packaging to obtain the bipolar lithium ion battery.
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| CN (1) | CN112582666A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114024037A (en) * | 2021-10-28 | 2022-02-08 | 中国第一汽车股份有限公司 | Solid-state battery cell, preparation method thereof and energy storage device |
| CN114552027A (en) * | 2021-09-14 | 2022-05-27 | 万向一二三股份公司 | Bipolar all-solid-state battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004164896A (en) * | 2002-11-11 | 2004-06-10 | Nissan Motor Co Ltd | Electrode for all-solid polymer battery and its manufacturing method |
| CN1985400A (en) * | 2004-12-07 | 2007-06-20 | 日产自动车株式会社 | Bipolar electrode batteries and methods of manufacturing bipolar electrode batteries |
| CN102117932A (en) * | 2009-12-31 | 2011-07-06 | 上海比亚迪有限公司 | Polymer electrolyte membrane and preparation method thereof, and polymer cell |
| KR20170037377A (en) * | 2015-09-25 | 2017-04-04 | 한국생산기술연구원 | CATHODE COMPOSITE MATERIAL FOR All SOLID LITHIUM SECONDARY BATTERY AND METHOD FOR PREPARING THE SAME |
| CN107591561A (en) * | 2017-08-03 | 2018-01-16 | 电子科技大学 | A kind of preparation method of lithium ion battery gel polymer electrolyte |
| CN108110257A (en) * | 2017-12-29 | 2018-06-01 | 暨南大学 | A kind of bipolar current collector and the bipolarity solid lithium secondary cell by its assembling |
| CN108110324A (en) * | 2017-11-17 | 2018-06-01 | 中国科学院深圳先进技术研究院 | A kind of preparation method of solid lithium ion battery |
| CN108649250A (en) * | 2018-03-30 | 2018-10-12 | 清陶（昆山）新能源材料研究院有限公司 | The baking process of pole piece-dielectric film integrated composite electrode in a kind of solid lithium battery |
| CN109659595A (en) * | 2017-10-11 | 2019-04-19 | 北京卫蓝新能源科技有限公司 | A kind of all-solid lithium-ion battery |
| CN109768334A (en) * | 2018-12-25 | 2019-05-17 | 中国电子科技集团公司第十八研究所 | Preparation method of bipolar solid-state lithium secondary battery |
| CN109980137A (en) * | 2017-11-03 | 2019-07-05 | 高级电池概念有限责任公司 | Bipolar cell component |
-
2019
- 2019-09-27 CN CN201910927310.0A patent/CN112582666A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004164896A (en) * | 2002-11-11 | 2004-06-10 | Nissan Motor Co Ltd | Electrode for all-solid polymer battery and its manufacturing method |
| CN1985400A (en) * | 2004-12-07 | 2007-06-20 | 日产自动车株式会社 | Bipolar electrode batteries and methods of manufacturing bipolar electrode batteries |
| CN102117932A (en) * | 2009-12-31 | 2011-07-06 | 上海比亚迪有限公司 | Polymer electrolyte membrane and preparation method thereof, and polymer cell |
| KR20170037377A (en) * | 2015-09-25 | 2017-04-04 | 한국생산기술연구원 | CATHODE COMPOSITE MATERIAL FOR All SOLID LITHIUM SECONDARY BATTERY AND METHOD FOR PREPARING THE SAME |
| CN107591561A (en) * | 2017-08-03 | 2018-01-16 | 电子科技大学 | A kind of preparation method of lithium ion battery gel polymer electrolyte |
| CN109659595A (en) * | 2017-10-11 | 2019-04-19 | 北京卫蓝新能源科技有限公司 | A kind of all-solid lithium-ion battery |
| CN109980137A (en) * | 2017-11-03 | 2019-07-05 | 高级电池概念有限责任公司 | Bipolar cell component |
| CN108110324A (en) * | 2017-11-17 | 2018-06-01 | 中国科学院深圳先进技术研究院 | A kind of preparation method of solid lithium ion battery |
| CN108110257A (en) * | 2017-12-29 | 2018-06-01 | 暨南大学 | A kind of bipolar current collector and the bipolarity solid lithium secondary cell by its assembling |
| CN108649250A (en) * | 2018-03-30 | 2018-10-12 | 清陶（昆山）新能源材料研究院有限公司 | The baking process of pole piece-dielectric film integrated composite electrode in a kind of solid lithium battery |
| CN109768334A (en) * | 2018-12-25 | 2019-05-17 | 中国电子科技集团公司第十八研究所 | Preparation method of bipolar solid-state lithium secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| 胡静: "《新材料》", 31 December 2011 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114552027A (en) * | 2021-09-14 | 2022-05-27 | 万向一二三股份公司 | Bipolar all-solid-state battery |
| CN114552027B (en) * | 2021-09-14 | 2023-09-05 | 万向一二三股份公司 | Bipolar all-solid-state battery |
| CN114024037A (en) * | 2021-10-28 | 2022-02-08 | 中国第一汽车股份有限公司 | Solid-state battery cell, preparation method thereof and energy storage device |
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