CN109216655B - Lithium slurry battery system with mutually independent charging and discharging - Google Patents
Lithium slurry battery system with mutually independent charging and discharging Download PDFInfo
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- CN109216655B CN109216655B CN201710550177.2A CN201710550177A CN109216655B CN 109216655 B CN109216655 B CN 109216655B CN 201710550177 A CN201710550177 A CN 201710550177A CN 109216655 B CN109216655 B CN 109216655B
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- positive electrode
- lithium
- cavity
- negative electrode
- slurry
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- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- JVZGJLAPJLXQKT-UHFFFAOYSA-N lithium iron(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical class [O-2].[Fe+2].[Mn+2].[Li+].[Ni+2] JVZGJLAPJLXQKT-UHFFFAOYSA-N 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
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- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
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- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical class [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium slurry battery system with mutually independent charge and discharge, which comprises: a positive electrode cavity in which positive electrode slurry is accommodated; a charging negative electrode chamber in which a first negative electrode active material layer is disposed; a first isolation layer located between the charged cathode cavity and the anode cavity; a discharge cathode chamber in which a second cathode active material layer is disposed; and the second isolating layer is positioned between the discharge cathode cavity and the anode cavity. During the charging process of the battery, lithium ions in the positive electrode slurry in the positive electrode cavity are extracted and embedded into the first negative electrode active material layer in the charging negative electrode cavity; during the discharge of the battery, lithium ions in the second negative active material layer in the discharge negative electrode cavity are extracted and inserted into the positive electrode slurry in the positive electrode cavity. The lithium slurry battery system with mutually independent charge and discharge is more flexible in operation and operation, is not limited by time and place, and can solve the safety problem that lithium dendrites generated by the traditional lithium slurry battery puncture an isolation layer.
Description
Technical Field
The invention relates to the field of energy storage batteries, in particular to a lithium slurry battery system with mutually independent charging and discharging.
Background
The new energy technologies such as solar energy, wind energy and the like have the characteristics of instability, discontinuity, uncontrollable and the like, and the energy storage technology is an effective measure for solving the problems. The electrochemical energy storage technology takes chemical elements as energy storage media, and the chemical reaction process of the energy storage media is accompanied in the charging and discharging process. A lithium paste battery is a new type of lithium battery. The reactor of the lithium slurry battery is internally provided with conductive slurry, the conductive slurry contains conductive particles which are suspended or precipitated in electrolyte in a certain proportion, and when the battery is impacted or vibrated from the outside, the conductive particles can move locally in the electrolyte to form a dynamic conductive network because the conductive particles are not bonded and fixed. The conductive paste in the lithium paste battery can avoid the problems of battery capacity reduction and cycle life attenuation caused by the falling or loosening of the electrode material of the traditional lithium battery, but the application in the field of large-scale energy storage is still to be developed.
At present, the lithium paste battery can be charged or discharged only for a certain period of time, like other conventional energy storage batteries, and thus the operating efficiency and the flexibility of use of the battery system are limited. In addition, lithium dendrite growth caused by the metallic lithium negative electrode also affects the safety and cycle life of the battery. In the process of charging and discharging of the battery, lithium dendrites grow on the surface of the metal lithium cathode, and when the lithium dendrites grow to a certain degree, the lithium dendrites can penetrate through a diaphragm, so that the safety problem is caused; in addition, lithium dendrite breakage can form "dead lithium" that results in a loss of battery capacity and affects battery cycle performance.
Disclosure of Invention
In view of the above problems, the present invention provides a lithium slurry battery system with independent charging and discharging, which includes a charging negative electrode chamber and a discharging negative electrode chamber that can be disposed in the same reactor housing or different reactor housings, so that the charging process and the discharging process of the battery system are independent from each other. In addition, in the charging negative electrode cavity, a protective layer can be arranged between the first isolation layer and the first lithium-containing metal body and is used for preventing the growth of lithium dendrites from puncturing the diaphragm in the charging process; in the discharge negative electrode cavity, an elastic body can be arranged on one side of the second lithium-containing metal body, which is far away from the second isolation layer, and the second lithium-containing metal body is continuously pushed to the second isolation layer through the elastic body along with the consumption of metal lithium in the discharge process, so that the increase of polarization internal resistance caused by the increase of a gap is avoided. This charge-discharge mutually independent lithium slurry battery system operation is more nimble, does not receive the restriction in time and place to can carry out independent structural design to charging negative pole chamber and discharging negative pole chamber, thereby solve the safety problem that the produced lithium dendrite of traditional lithium slurry battery punctures the isolation layer.
The purpose of the invention is realized by the following modes:
a lithium slurry battery system which is independently charged and discharged, a reactor of the lithium slurry battery system comprising: a positive electrode chamber in which positive electrode slurry is accommodated; a charging negative electrode cavity in which a first negative electrode active material layer is disposed; a first isolation layer located between the charged cathode cavity and the anode cavity; a discharge cathode cavity in which a second cathode active material layer is disposed; and a second isolation layer located between the discharge cathode cavity and the anode cavity. During the charging process of the battery, lithium ions in the positive electrode slurry in the positive electrode cavity are extracted and are embedded into the first negative electrode active material layer in the charging negative electrode cavity; in the discharging process of the battery, lithium ions in the second negative active material layer in the discharging negative electrode cavity are extracted and inserted into the positive slurry in the positive electrode cavity, so that the charging process and the discharging process of the lithium slurry battery system are independent.
The first negative active material layer and the second negative active material layer may be one or more of a negative electrode slurry, a negative active material coating layer, and a lithium-containing metal body. The negative electrode slurry is prepared by dispersing negative electrode conductive particles in electrolyte, and the thickness of the negative electrode slurry layer can be 0.5-10 mm. The average particle size of the negative electrode conductive particles can be 0.05-500 microns, the negative electrode conductive particles are a compound or a mixture of a negative electrode active material and a conductive agent, and the mass ratio of the negative electrode active material to the conductive agent is preferably 20-98: 80-2. The negative active material is one or more of aluminum-based alloy, silicon-based alloy, tin-based alloy, lithium titanium oxide, lithium silicon oxide, metal lithium powder and graphite which can be embedded with lithium; the conductive agent can be one or more of carbon black, ketjen black, graphene, carbon nanotubes, carbon fibers, amorphous carbon, graphene and metal conductive particles. The negative active material coating layer is formed by coating negative conductive particles on a current collecting layer, the total thickness of the coating is 0.05-2.5 mm, the porosity is 10-90%, and the average pore size range is 0.001-10 μm. The material of the lithium-containing metal body may be metallic lithium or a lithium-based alloy. The lithium-based alloy can be Li-Al, Li-Si, Li-Mg, Li-Sn, Li-Bi, Li-Sb, etc., can be binary, ternary or multicomponent alloy, and can include Mg, Ca, Al, Si, Ge, Sn, Pb, As, Sb, Bi, Pt, Ag, Au, Zn, Cd, Hg, etc. elements capable of carrying out solid solution and/or addition reaction with lithium, wherein the content of non-lithium elements is not more than 50%.
The positive electrode slurry is formed by dispersing positive electrode conductive particles in electrolyte, and the thickness of a positive electrode slurry layer can be 0.5-10 mm. The average particle size of the positive conductive particles can be 0.05-500 mu m, the positive conductive particles are a compound or a mixture of a positive active material and a conductive agent, and the mass ratio of the positive active material to the conductive agent is preferably 20-98: 80-2. The positive active material is a compound capable of providing lithium ions, and includes one or more of lithium iron phosphate, lithium manganese phosphate, lithium silicate, lithium iron silicate, sulfate compounds, sulfur-carbon compounds, elemental sulfur, titanium sulfur compounds, molybdenum sulfur compounds, iron sulfur compounds, doped lithium manganese oxides, lithium cobalt oxides, lithium titanium oxides, lithium vanadium oxides, lithium nickel manganese oxides, lithium nickel cobalt aluminum oxides, lithium nickel cobalt manganese oxides, lithium iron nickel manganese oxides, other lithium-intercalatable compounds, and the like. The conductive agent can be one or more of carbon black, graphene, carbon nanotubes, carbon fibers, amorphous carbon, metal conductive particles and the like.
Preferably, the first negative electrode active material layer is a first lithium-containing metal body, and a protective layer for preventing lithium dendrites from puncturing the first isolation layer is further disposed in the charging negative electrode cavity, and the protective layer is disposed between the first isolation layer and the first lithium-containing metal body; the second negative active material layer is a second lithium-containing metal body, an elastic body used for pushing the second lithium-containing metal body to abut against the second isolation layer is further arranged in the discharge negative electrode cavity, and the elastic body is arranged on one side, which is not in contact with the second isolation layer, of the second lithium-containing metal body. The first lithium-containing metal body may have a thickness of 0.5mm to 10mm, and the second lithium-containing metal body may have a thickness of 0.5mm to 10 mm. The thickness of the first lithium-containing metal body is preferably smaller than the thickness of the second lithium-containing metal body. When the battery is charged, lithium ions in the positive electrode active material of the positive electrode slurry are embedded into the first lithium-containing metal body of the charging negative electrode cavity through the first isolation layer, the charged positive electrode active material is in a lithium-removed state, and after multiple times of charging, the first lithium-containing metal body can be subjected to surface polishing treatment, so that maintenance and regeneration of a system are completed or the first lithium-containing metal body can be subjected to material recovery and regeneration. When the battery discharges, lithium ions in the second lithium-containing metal body of the discharging negative electrode cavity are embedded into the positive electrode active material of the positive electrode slurry through the second isolation layer, the positive electrode active material is in a lithium embedded state after discharging, the second lithium-containing metal body is continuously consumed after discharging for many times, but the second lithium-containing metal body is always in contact with the second isolation layer under the pushing of the elastic body, and the second lithium-containing metal body can be replaced and supplemented to maintain and regenerate the system after being consumed to a certain degree.
The safety of the battery system may be achieved by a protective layer disposed in the charging negative electrode chamber. The protective layer may be an isolation cavity filled with an electrolyte, and the height of the isolation cavity may be, for example, 0.05mm to 1 mm. In addition, an additive for improving the interface stability of the lithium-containing metal body and/or inhibiting the growth of lithium dendrites can be added into the electrolyte of the isolation cavity, the additive can be a metal cation with a reduction potential lower than that of lithium ions, and the metal cation can comprise alkali metal ions Cs +, Rb + and the like; alternatively, the additive may be an organic additive, which may include a small molecule-based additive, which may include fluoroethylene carbonate (FEC), Vinylene Carbonate (VC), and Ethylene Sulfite (ES), or a polymer-based additive, which may include polyvinylpyrrolidone (PVP), Polyacrylonitrile (PAN), and polyethylene oxide (PEO), or the like; alternatively, the additive may be an ionic liquid, and ions in the ionic liquid may include cations such as imidazoles, pyrroles, pyridines, quaternary amines, and anions such as hexafluorophosphoric acid, fluoroboric acid, sulfonic acid, and derivatives thereof. Alternatively, the protective layer may be a porous insulating isolation layer, the thickness of the porous insulating isolation layer may be, for example, 0.005mm to 1mm, and the material of the porous insulating isolation layer may be an electronically nonconductive polymer material and/or an electronically nonconductive inorganic nonmetallic material. The electronic non-conductive polymer material can be one or more of polyethylene, polypropylene, polyvinylidene fluoride and the like, and the electronic non-conductive inorganic non-metallic material can be one or more of glass fiber non-woven fabric, synthetic fiber non-woven fabric, ceramic fiber paper and the like.
In order to avoid polarization internal resistance increase caused by the increase of the gap between the second lithium-containing metal body and the second isolation layer in the discharge negative electrode cavity, an elastic body is arranged in the discharge negative electrode cavity and is positioned on one side of the second lithium-containing metal body, which is not in contact with the second isolation layer. The elastic body is in a compressed state before the battery is discharged and gradually rebounds along with the gradual progress of the discharge process, and the elastic body applies pressure to the second lithium-containing metal body so as to avoid a gap between the second lithium-containing metal body and the second isolation layer. The elastomer has good elasticity, and the distance change range can be 0.5 mm-100 mm. The elastic body can be an elastic support body made of elastic materials, the elastic support body comprises a thermoplastic elastic body and a thermosetting elastic body, the thermoplastic elastic body can comprise polyolefin, modified polyurethane, polystyrene, polyamide and the like, and the thermosetting elastic body can comprise styrene butadiene rubber, isoprene rubber, ethylene propylene diene monomer rubber, butyl rubber, chloroprene rubber, fluororubber, corrosion-resistant silicone rubber and the like. Alternatively, the elastic body may be a spring, the material of the spring may be a metal material or a non-metal material which is resistant to electrolyte corrosion, the metal material may include stainless steel, copper, nickel, titanium, and the like, and an alloy material made of the above metal materials, and the non-metal material may include resin, rubber, plastic, and the like.
The positive electrode cavity is provided with a positive electrode current collecting layer, and the positive electrode current collecting layer can be an electronic conducting layer with the thickness of 1-2000 mu m, preferably 0.05-1000 mu m. The positive current collecting layer is preferably an electronic conducting layer with a through hole structure, the aperture can be 0.01-2000 μm, preferably 10-1000 μm, and the porosity of the through hole can be 10-90%. The positive current collecting layer can be a conductive metal layer, the conductive metal layer is a metal net, a metal wire woven net, a porous metal plate or a porous metal foil, and meshes can be square, rhombic, rectangular or polygonal; or the conductive metal layer is a foam metal net with a through hole structure; alternatively, the conductive metal layer is a metal plate or a metal foil, and the material of the conductive metal layer may be stainless steel, aluminum, silver, or the like. Or the positive current collecting layer can be carbon fiber conductive cloth or conductive cloth mixed by metal wires and organic fiber wires, the metal wires can be made of aluminum, alloy aluminum, stainless steel or silver, and the organic fiber wires can comprise one or more of natural cotton hemp, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene, polytetrafluoroethylene and the like. Or, the positive current collecting layer is a metal conductive layer with a conductive coating or a metal film coated on the surface, a conductive cloth, an inorganic non-metallic material and a porous organic material, the conductive coating is a mixture of a conductive agent and a binder or the conductive coating is a mixture of a conductive agent, a positive active material and a binder, the mixing mode is bonding, spraying, evaporation or mechanical pressing, the porous organic material comprises natural cotton-flax, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene and polytetrafluoroethylene, the inorganic non-metallic material comprises glass fiber non-woven fabric and ceramic fiber paper, the conductive agent is one or more of carbon black, ketjen black, graphene, carbon nanotubes, carbon fibers, amorphous carbon, metal conductive particles and metal conductive fibers, the metal conductive particles or the metal conductive fibers can be aluminum, stainless steel or silver, and the binder can be polyvinyl chloride, stainless steel, silver, and the like, One or more of polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyester terephthalate, polyamide, polyimide, polyether nitrile, polymethyl acrylate, polyvinylidene fluoride, polyurethane, polyacrylonitrile, styrene-butadiene rubber, sodium carboxymethylcellulose and modified polyolefin. Or the positive current collecting layer is a combination of any two or more of the above. And the positive electrode current collecting layer is connected with a positive electrode lug.
The negative current collecting layer can be an electronic conducting layer with the thickness of 1-2000 mu m, preferably 0.05-1000 mu m, and the negative current collecting layer is preferably an electronic conducting layer with a through hole structure, the pore diameter can be 0.01-2000 mu m, preferably 10-1000 mu m, and the porosity of the through hole can be 10-90%. The negative current collecting layer can be a conductive metal layer, the conductive metal layer can be a metal net, a metal wire woven net, a porous metal plate or a porous metal foil, and meshes can be square, rhombic, rectangular or polygonal; alternatively, the conductive metal layer may be a porous foam metal layer having a porous structure; alternatively, the conductive metal layer may be a metal plate or a metal foil, and the material of the conductive metal layer may be stainless steel, nickel, titanium, tin-plated copper, nickel-plated copper, or the like. Or the negative current collecting layer can be carbon fiber conductive cloth or conductive cloth mixed by metal wires and organic fiber wires, and the metal wires can be made of stainless steel, nickel, titanium, tin-plated copper or nickel-plated copper and the like; the organic fiber yarn comprises one or more of natural cotton and hemp, terylene, aramid fiber, nylon, polypropylene fiber, polyethylene and polytetrafluoroethylene. Or, the negative current collecting layer may be a metal conductive layer with a conductive coating or a metal film coated on the surface, a conductive cloth, an inorganic non-metallic material, a porous organic material, the conductive coating may be a composite of a conductive agent and a binder or a conductive agent, and a negative electrode lithium-embeddable material and a binder, the composite mode may be bonding, spraying, evaporation, mechanical pressing, or the like, the porous organic material may include natural cotton, polyester, aramid, nylon, polypropylene, polyethylene, polytetrafluoroethylene, or the like, the inorganic non-metallic material may include glass fiber non-woven fabric, ceramic fiber paper, or the like, the conductive film may be stainless steel, nickel, titanium, tin-plated copper, nickel-plated copper, or the like, the conductive agent may be one or more of carbon black, ketjen black, graphene, carbon nanotubes, carbon fibers, amorphous carbon, metal conductive particles, and metal conductive fibers, and the metal conductive particles or metal conductive fibers may be aluminum, Stainless steel or silver, etc., and the binder may be one or more of polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyester terephthalate, polyamide, polyimide, polyether nitrile, polymethyl acrylate, polyvinylidene fluoride, polyurethane, polyacrylonitrile, styrene butadiene rubber, sodium carboxymethylcellulose and modified polyolefin. Alternatively, the negative current collector layer may be a combination of any two or more of the above. The negative electrode tab may be attached to the negative electrode current collector layer and/or the lithium-containing metal body.
The material of the isolating layer can be an electronic non-conducting porous polymer material; or the material of the isolation layer can be a porous material compounded by an electronic non-conductive inorganic non-metallic material and an organic polymer; or the material of the isolating layer can be a gel polymer electrolyte composite material formed by compounding an electronic non-conducting polymer matrix, a liquid organic plasticizer and lithium salt; alternatively, the material of the isolation layer may be an electrolyte or a polymer colloid material which is impregnated with ionic conduction in the pores of a porous polymer material which is not electronically conductive or in the pores of a porous material which is a composite of an inorganic non-metallic material and an organic polymer, or the like.
The positive electrode cavity, the charging negative electrode cavity and the discharging negative electrode cavity of the lithium slurry battery system can be arranged in the same reactor shell, and the positive electrode cavity is positioned between the charging negative electrode cavity and the discharging negative electrode cavity. In this case, the charging process of the battery is completed between the positive electrode chamber and the charging negative electrode chamber, and the discharging process of the battery is completed between the positive electrode chamber and the discharging negative electrode chamber. The charging and discharging processes share the same positive chamber, but use different negative chambers. Because different negative electrode cavities are used, the negative electrode active materials and the structures in the charging negative electrode cavity and the discharging negative electrode cavity can be independent of each other without being influenced by each other. When the battery is charged, a positive electrode tab connected with the positive electrode cavity is electrically connected to the negative electrode of the power supply, and a negative electrode tab connected with the charged negative electrode cavity is electrically connected to the positive electrode of the power supply; when the battery discharges, the anode tab connected with the anode cavity is electrically connected with the anode of the load, and the cathode tab connected with the discharging cathode cavity is electrically connected with the cathode of the load. By the lithium slurry battery system, the safety performance of the system can be ensured under the condition that the charging negative electrode cavity and the discharging negative electrode cavity are respectively subjected to structural design, the battery system is compact in structure, extra required driving equipment caused by electrode slurry flowing is avoided, and the energy consumption of the system is reduced.
In addition, the lithium paste battery system according to the present invention can completely separate the charging process from the discharging process. Specifically, a charge positive electrode chamber and a charge negative electrode chamber are provided in the charge reactor case, and a discharge positive electrode chamber and a discharge negative electrode chamber are provided in the discharge reactor case. The charging positive electrode cavity is used for containing positive electrode slurry embedded with lithium, and the discharging positive electrode cavity is used for containing positive electrode slurry removed with lithium. In this case, the charging of the battery is completed in a charging reactor provided with a charging anode chamber and a charging cathode chamber, and the discharging of the battery is completed in a discharging reactor provided with a discharging anode chamber and a discharging cathode chamber, the charging reactor and the discharging reactor are independent from each other, and the charging process and the discharging process can be performed simultaneously or non-simultaneously, and performed simultaneously or in different places. The lithium paste battery system not only can ensure the safety of the battery system, but also has great operation flexibility. The positive electrode slurry in the charging positive electrode cavity and the discharging positive electrode cavity can be directly communicated through a pipeline or can be transported in different places through an independent storage device.
The first conveying pipeline is used for conveying the anode slurry which is subjected to lithium removal in the charging anode cavity to the discharging anode cavity, and the second conveying pipeline is used for conveying the anode slurry which is subjected to lithium embedding in the discharging anode cavity to the charging anode cavity. The first conveying pipeline and the second conveying pipeline can be fixedly connected with the charging positive electrode cavity and the discharging positive electrode cavity, or the first conveying pipeline and the second conveying pipeline can be connected with and disconnected from the charging positive electrode cavity and the discharging positive electrode cavity through interfaces. In addition, a first positive electrode slurry storage device for storing the positive electrode slurry from which lithium has been removed in the charging positive electrode chamber may be provided in the first transport line, and a second positive electrode slurry storage device for storing the positive electrode slurry from which lithium has been embedded in the discharging positive electrode chamber may be provided in the second transport line. Through the first positive electrode slurry storage device and the second positive electrode slurry storage device, the lithium-removed or lithium-inserted positive electrode slurry can be stored in the storage device without directly entering the reactor, so that the ongoing reaction process in the charging reactor or the discharging reactor can not be influenced, and the charging process and the discharging process are independent of each other and cannot be influenced with each other.
The lithium slurry battery system can comprise a lithium-removed positive electrode slurry storage device and a lithium-embedded positive electrode slurry storage device, wherein the lithium-removed positive electrode slurry storage device can be in fluid communication with or disconnected from a charging positive electrode cavity through an interface and can convey lithium-removed positive electrode slurry in the charging positive electrode cavity into the lithium-removed positive electrode slurry storage device through a driving device, and the lithium-removed positive electrode slurry storage device can be in fluid communication with or disconnected from a discharging positive electrode cavity through the interface and can convey lithium-removed positive electrode slurry in the lithium-removed positive electrode slurry storage device into the discharging positive electrode cavity through the driving device; the lithium-intercalated positive electrode slurry storage device can be in fluid communication with or disconnected from the discharge positive electrode cavity through the interface and can convey the lithium-intercalated positive electrode slurry in the discharge positive electrode cavity to the lithium-intercalated positive electrode slurry storage device through the driving device, and the lithium-intercalated positive electrode slurry storage device can be in fluid communication with or disconnected from the charge positive electrode cavity through the interface and can convey the lithium-intercalated positive electrode slurry in the lithium-intercalated positive electrode slurry storage device to the charge positive electrode cavity through the driving device. Through the independent lithium-removed positive electrode slurry storage device and the independent lithium-embedded positive electrode slurry storage device, the charging and the discharging of the lithium slurry battery can be respectively carried out at different places.
The invention has the advantages that:
1) flexibility: the design of the charging reactor and the discharging reactor which are independent from each other enables the battery to have higher use flexibility.
2) Energy density: the use of a lithium-containing metal body, such as lithium metal, as the negative electrode provides a higher energy density.
3) Safety: the charging reactor and the discharger are respectively designed according to different reaction characteristics of the negative electrode, so that the safety problem caused by the growth of the lithium dendrite is avoided.
Drawings
Fig. 1 is a schematic view of a lithium paste battery system according to a first embodiment of the present invention;
fig. 2 is a schematic view of a lithium paste battery system according to a second embodiment of the present invention;
fig. 3 is a schematic view of a lithium paste battery system according to a third embodiment of the present invention.
List of reference numerals
1-reactor housing
101-charging reactor shell
102-discharge reactor shell
2-Positive electrode Chamber
201-positive electrode cavity of charging
202-discharge anode chamber
3-positive current collecting layer
301-first positive current collector layer
302-second positive current collector layer
4-positive pole ear
401-first positive pole tab
402-second positive electrode tab
501-charging cathode cavity
502-discharge cathode cavity
601-first negative current collector layer
602-second negative current collector layer
701 — first lithium-containing metal body
702-second lithium-containing metal body
801-first negative pole tab
802-second negative pole tab
901 first insulating layer
902-second spacer layer
10 protective layer
11-Elastomers
1201-first transfer line
1202-second transfer line
1301 — first positive electrode paste storage device
1302-second positive paste storage device
1401-charging reactor interface
1402-discharge reactor interface
1501-lithium-removed anode slurry storage device
1502-embedded lithium anode slurry storage device
Detailed Description
The invention will be further explained by embodiments in conjunction with the drawings.
Fig. 1 is a schematic view of a lithium paste battery system according to a first embodiment of the present invention. The lithium paste battery system includes: the lithium ion battery comprises a reactor shell 1, a positive electrode cavity 2, a positive electrode current collecting layer 3, a positive electrode tab 4, a charging negative electrode cavity 501, a discharging negative electrode cavity 502, a first lithium-containing metal body 701, a first negative electrode tab 801, a first isolating layer 901, a protective layer 10, a second lithium-containing metal body 702, a second negative electrode tab 802, a second isolating layer 902 and an elastic body 11. The anode cavity 2 is located in the middle of the reactor housing 1, the anode cavity 2 is separated from the charging cathode cavity 501 by a first isolation layer 901, and the anode cavity 2 is separated from the discharging cathode cavity 502 by a second isolation layer 902. The positive electrode cavity 2 is provided with positive electrode slurry and a positive electrode current collecting layer 3, and a positive electrode tab 4 is electrically connected to the positive electrode current collecting layer 3. A first lithium-containing metal body 701 and a protective layer 10 are arranged in the charging negative electrode cavity 501, the protective layer 10 is an isolation cavity filled with electrolyte, the height h of the isolation cavity is 0.5mm, the thickness of the first lithium-containing metal body 701 is 1.5mm, and a first negative electrode tab 801 is electrically connected to the first lithium-containing metal body 701. A second lithium-containing metal body 702 and an elastic body 11 are provided in the discharge negative electrode chamber 502, the elastic body 11 is rubber in an initial state of a compressed state, the thickness of the second lithium-containing metal body 702 is 50mm, and a second negative electrode tab 802 is electrically connected to the second lithium-containing metal body 702.
In the process of charging the battery, the positive electrode tab 4 is electrically connected to the negative electrode of the power supply, the first negative electrode tab 801 is electrically connected to the positive electrode of the power supply, lithium ions in the positive electrode active material of the positive electrode slurry are embedded into the first lithium-containing metal body 701, the protective layer 10 can prevent lithium dendrites generated on the first lithium-containing metal body 701 from puncturing the first isolation layer 901, and the charged positive electrode active material is in a delithiated state. During the discharging process of the battery, the positive electrode tab 4 is electrically connected to the positive electrode of the load, the second negative electrode tab 802 is electrically connected to the negative electrode of the load, the lithium ions in the second lithium-containing metal body 702 are embedded into the positive electrode active material of the positive electrode slurry, the elastic body 11 can gradually rebound along with the thickness reduction of the second lithium-containing metal body 702 and continuously push the second lithium-containing metal body 702 to abut against the second isolation layer 902, and the discharged positive electrode active material is in a lithium embedded state.
Fig. 2 is a schematic view of a lithium paste battery system according to a second embodiment of the present invention. The lithium paste battery system includes: the lithium ion battery charging reactor comprises a charging reactor shell 101, a charging positive electrode cavity 201, a first positive electrode current collecting layer 301, a first positive electrode tab 401, a charging negative electrode cavity 501, a first negative electrode current collecting layer 601, a first lithium-containing metal body 701, a first negative electrode tab 801, a first isolation layer 901, a protection layer 10, a discharging reactor shell 102, a discharging positive electrode cavity 202, a second positive electrode current collecting layer 302, a second positive electrode tab 402, a discharging negative electrode cavity 502, a second negative electrode current collecting layer 602, a second lithium-containing metal body 702, a second negative electrode tab 802, a second isolation layer 902, an elastic body 11, a first conveying pipeline 1201, a second conveying pipeline 1202, a first positive electrode slurry storage device 1301 and a second positive electrode slurry storage device 1302. The charging positive electrode cavity 201 and the charging negative electrode cavity 501 are arranged in the charging reactor shell 101 and are separated by a first isolation layer 901, positive electrode slurry embedded with lithium and a first positive electrode current collecting layer 301 are arranged in the charging positive electrode cavity 201, a first positive electrode tab 401 is electrically connected to the first positive electrode current collecting layer 301, a first lithium-containing metal body 701 and a protection layer 10 are arranged in the charging negative electrode cavity 501, the protection layer 10 is a porous insulation isolation layer with the thickness of 1mm, the thickness of the first lithium-containing metal body 701 is 0.5mm, and the first negative electrode tab 801 is electrically connected to the first negative electrode current collecting layer 601. The discharge anode cavity 202 and the discharge cathode cavity 502 are disposed in the discharge reactor shell 102 and separated by a second isolation layer 902, a delithiated anode slurry and a second anode current collector layer 302 are disposed in the discharge anode cavity 202, a second anode tab 402 is electrically connected to the second anode current collector layer 302, a second lithium-containing metal body 702 and an elastic body 11 are disposed in the discharge cathode cavity 502, the elastic body 11 is a stainless steel spring in an initial state of a compressed state, the thickness of the second lithium-containing metal body 702 is 80mm, and a second cathode tab 802 is electrically connected to the second cathode current collector layer 602.
In the charging reactor, a first positive electrode tab 401 is electrically connected to the negative electrode of the power supply, a first negative electrode tab 801 is electrically connected to the positive electrode of the power supply, lithium ions in the positive electrode active material in which the lithium positive electrode slurry has been embedded are embedded in the first lithium-containing metal body 701, and the charged positive electrode active material is in a delithiated state. The delithiated positive electrode slurry is transferred to the first positive electrode slurry storage device 1301 through the first transfer line 1201 and further transferred to the discharge positive electrode chamber 202. In the discharge reactor, a second positive electrode tab 402 is electrically connected to a positive electrode of a load, a second negative electrode tab 802 is electrically connected to a negative electrode of the load, lithium ions in the second lithium-containing metal body 702 are intercalated into a positive electrode active material of the delithiated positive electrode slurry, and the discharged positive electrode active material is in a lithium intercalation state. The lithium-intercalated positive electrode slurry is transported to the second positive electrode slurry storage device 1302 via the second transport pipe 1202 and further transported to the charging positive electrode chamber 201.
Fig. 3 is a schematic view of a lithium paste battery system according to a third embodiment of the present invention. The lithium paste battery system includes: the lithium ion battery charging system comprises a charging reactor shell 101, a charging positive electrode cavity 201, a first positive electrode current collecting layer 301, a first positive electrode tab 401, a charging negative electrode cavity 501, a first negative electrode current collecting layer 601, a first lithium-containing metal body 701, a first negative electrode tab 801, a first isolating layer 901, a protective layer 10, a charging reactor interface 1401, a discharging reactor shell 102, a discharging positive electrode cavity 202, a second positive electrode current collecting layer 302, a second positive electrode tab 402, a discharging negative electrode cavity 502, a second negative electrode current collecting layer 602, a second lithium-containing metal body 702, a second negative electrode tab 802, a second isolating layer 902, an elastic body 11, a discharging reactor interface 1402, a lithium-removed positive electrode slurry storage device 1501 and a lithium-embedded positive electrode slurry storage device 1502. The charging positive electrode cavity 201 and the charging negative electrode cavity 501 are arranged in the charging reactor shell 101 and are separated by a first isolation layer 901, positive electrode slurry embedded with lithium and a first positive electrode current collecting layer 301 are arranged in the charging positive electrode cavity 201, a first positive electrode tab 401 is electrically connected to the first positive electrode current collecting layer 301, a first lithium-containing metal body 701 and a protection layer 10 are arranged in the charging negative electrode cavity 501, the protection layer 10 is an isolation cavity with the height of 0.1mm, the isolation cavity is filled with electrolyte and added with alkali metal ions Cs +, the thickness of the first lithium-containing metal body is 2mm, and the first negative electrode tab 801 is electrically connected to the first negative electrode current collecting layer 601. The discharge anode cavity 202 and the discharge cathode cavity 502 are disposed in the discharge reactor shell 102 and separated by a second isolation layer 902, a delithiated anode slurry and a second anode current collector layer 302 are disposed in the discharge anode cavity 202, a second anode tab 402 is electrically connected to the second anode current collector layer 302, a second lithium-containing metal body 702 and an elastic body 11 are disposed in the discharge cathode cavity 502, the elastic body 11 is a polyolefin elastic body in an initial state of a compressed state, the thickness of the second lithium-containing metal body 702 is 50mm, and a second cathode tab 802 is electrically connected to the second cathode current collector layer 602.
In the charging reactor, a first positive electrode tab 401 is electrically connected to the negative electrode of the power supply, a first negative electrode tab 801 is electrically connected to the positive electrode of the power supply, lithium ions in the positive electrode active material embedded with the lithium positive electrode slurry are embedded in the first lithium-containing metal body, and the charged positive electrode active material is in a delithiated state. The interface of the delithiated positive electrode slurry storage device 1501 is interfaced with the charging reactor interface 1401, the delithiated positive electrode slurry is transferred into the delithiated positive electrode slurry storage device 1501, and then the interface is disconnected and sealed. An interface of a delithiated positive electrode slurry storage device 1501 storing delithiated positive electrode slurry may interface with discharge reactor interface 1402 to deliver the delithiated positive electrode slurry into discharge positive electrode chamber 202. In the discharge reactor, a second positive electrode tab 402 is electrically connected to a positive electrode of a load, a second negative electrode tab 802 is electrically connected to a negative electrode of the load, lithium ions in the second lithium-containing metal body 702 are intercalated into a positive electrode active material of the delithiated positive electrode slurry, and the discharged positive electrode active material is in a lithium intercalation state. The interface of the lithium-intercalated positive electrode slurry storage device 1502 is butted with the discharge reactor interface 1402, the lithium-intercalated positive electrode slurry is conveyed into the lithium-intercalated positive electrode slurry storage device 1502, and then the interface is disconnected and sealed. The interface of the intercalated lithium positive electrode slurry storage device 1502 storing the intercalated lithium positive electrode slurry may be interfaced with the charging reactor interface 1401 to deliver the intercalated lithium positive electrode slurry into the charging positive electrode cavity 201.
The specific embodiments of the present invention are not intended to be limiting of the invention. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments, using the methods and techniques disclosed above, without departing from the scope of the present invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (8)
1. A lithium slurry battery system that is independently charged and discharged, wherein a reactor of the lithium slurry battery system comprises: a positive electrode chamber in which positive electrode slurry is accommodated; a charging negative electrode cavity in which a first negative electrode active material layer is disposed; a first isolation layer located between the charged negative electrode cavity and the positive electrode cavity; a discharge cathode cavity in which a second cathode active material layer is disposed; a second isolation layer located between the discharge negative electrode cavity and the positive electrode cavity, wherein, during the charging process of the battery, lithium ions in the positive electrode slurry in the positive electrode cavity are extracted and embedded into the first negative electrode active material layer in the charge negative electrode cavity, during the discharging process of the battery, lithium ions in the second negative electrode active material layer in the discharge negative electrode cavity are extracted and embedded into the positive electrode slurry in the positive electrode cavity, so that the charging process and the discharging process of the lithium slurry battery system are mutually independent, the first negative electrode active material layer is a first lithium-containing metal body, a protection layer for preventing lithium dendrites from puncturing the first isolation layer is further arranged in the charge negative electrode cavity, the protection layer is arranged between the first isolation layer and the first lithium-containing metal body, the second negative electrode active material layer is a second metal body, and a protection layer for pushing the second lithium-containing metal body to be tightly close to the lithium-containing metal body is further arranged in the discharge negative electrode cavity An elastic body of the second separator layer, the elastic body being disposed on a side of the second lithium-containing metal body that is not in contact with the second separator layer,
the positive electrode cavity, the charging negative electrode cavity and the discharging negative electrode cavity are arranged in the same reactor shell, and the positive electrode cavity is positioned between the charging negative electrode cavity and the discharging negative electrode cavity; or, the positive pole chamber is including the anodal chamber that charges and the anodal chamber that discharges, the anodal chamber that charges is used for the positive pole thick liquids that the holding has inlayed lithium and the anodal chamber that discharges is used for the positive pole thick liquids that the holding has taken off the lithium, the anodal chamber that charges with the negative pole chamber that charges sets up in the reactor shell that charges, the anodal chamber that discharges with the negative pole chamber that discharges sets up in the reactor shell that discharges.
2. The lithium paste battery system according to claim 1, wherein the protective layer is an isolation cavity filled with an electrolyte, and the height of the isolation cavity is 0.05mm to 1 mm; or,
the protective layer is a porous insulating isolation layer, the thickness of the porous insulating isolation layer is 0.005 mm-1 mm, and the porous insulating isolation layer is made of an electronic non-conductive polymer material and/or an electronic non-conductive inorganic non-metal material.
3. The lithium slurry battery system according to claim 2, wherein an additive for improving the interface stability of the lithium-containing metal body and/or inhibiting the growth of lithium dendrites is added to the electrolyte of the separation chamber, the additive being a metal cation having a lower reduction potential than lithium ions, the metal cation comprising alkali metal ions Cs +, Rb +; or the additive is an organic additive, the organic additive comprises a small molecule additive or a polymer additive, the small molecule additive comprises fluoroethylene carbonate, vinylene carbonate and ethylene glycol sulfite, and the polymer additive comprises polyvinylpyrrolidone, polyacrylonitrile and polyethylene oxide; or the additive is ionic liquid, and ions in the ionic liquid comprise imidazole, pyrrole, pyridine, quaternary ammonium cations, hexafluorophosphoric acid, fluoroboric acid, sulfonic acid and derivative anions thereof.
4. The lithium paste battery system according to claim 2, wherein the polymer material is one or more of polyethylene, polypropylene and polyvinylidene fluoride, and the inorganic non-metallic material is one or more of glass fiber non-woven fabric, synthetic fiber non-woven fabric and ceramic fiber paper.
5. The lithium paste battery system according to claim 1, wherein the elastic body is in a compressed state before the battery is discharged and gradually rebounds as the discharge process progresses, and the pressure is applied to the second lithium-containing metal body by the elastic body to avoid a gap between the second lithium-containing metal body and the second separator,
the elastic body is an elastic supporting body made of an elastic material, the elastic supporting body comprises a thermoplastic elastomer and a thermosetting elastomer, the thermoplastic elastomer comprises polyolefin, modified polyurethane, polystyrene and polyamide, and the thermosetting elastomer comprises styrene-butadiene rubber, isoprene rubber, ethylene propylene diene monomer, butyl rubber, chloroprene rubber, fluorine rubber and corrosion-resistant silicon rubber; or the elastic body is a spring, the spring is made of a metal material or a non-metal material which is resistant to electrolyte corrosion, the metal material comprises stainless steel, copper, nickel, titanium and an alloy material made of the metal materials, and the non-metal material comprises resin, rubber and plastics.
6. The lithium paste battery system according to claim 1, wherein a first transfer line and a second transfer line are provided between the charging positive electrode chamber and the discharging positive electrode chamber, the first transfer line being configured to transfer the delithiated positive electrode paste in the charging positive electrode chamber into the discharging positive electrode chamber, the second transfer line being configured to transfer the lithium-embedded positive electrode paste in the discharging positive electrode chamber into the charging positive electrode chamber.
7. The lithium slurry battery system according to claim 6, wherein a first positive electrode slurry storage device is provided in the first transport line to store the positive electrode slurry in which lithium has been removed in the charging positive electrode chamber, and a second positive electrode slurry storage device is provided in the second transport line to store the positive electrode slurry in which lithium has been embedded in the discharging positive electrode chamber.
8. The lithium slurry battery system according to claim 1, wherein the lithium slurry battery system comprises a delithiated positive electrode slurry storage device and a lithium-intercalated positive electrode slurry storage device, the delithiated positive electrode slurry storage device is capable of being in fluid communication with or disconnected from the charging positive electrode cavity through an interface and is capable of transporting delithiated positive electrode slurry in the charging positive electrode cavity into the delithiated positive electrode slurry storage device through a drive device, and the delithiated positive electrode slurry storage device is capable of being in fluid communication with or disconnected from the discharging positive electrode cavity through an interface and is capable of transporting delithiated positive electrode slurry in the delithiated positive electrode slurry storage device into the discharging positive electrode cavity through a drive device;
the lithium-intercalated positive electrode slurry storage device can be in fluid communication with or disconnected from the discharge positive electrode cavity through an interface and can convey the lithium-intercalated positive electrode slurry in the discharge positive electrode cavity into the lithium-intercalated positive electrode slurry storage device through a driving device, and the lithium-intercalated positive electrode slurry storage device can be in fluid communication with or disconnected from the charge positive electrode cavity through an interface and can convey the lithium-intercalated positive electrode slurry in the lithium-intercalated positive electrode slurry storage device into the charge positive electrode cavity through a driving device.
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| CN112216812B (en) * | 2019-07-10 | 2022-02-08 | 比亚迪股份有限公司 | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile |
| CN112216878B (en) * | 2019-07-10 | 2021-11-12 | 比亚迪股份有限公司 | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile |
| CN110518189B (en) * | 2019-10-23 | 2020-02-14 | 湖南省正源储能材料与器件研究所 | Device and method for simultaneously realizing pre-deoxidation of anode material and pre-lithiation of cathode material |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
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