CN117477049A - Battery capable of absorbing and dredging gas and battery cell comprising same - Google Patents
Battery capable of absorbing and dredging gas and battery cell comprising same Download PDFInfo
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- CN117477049A CN117477049A CN202311832510.0A CN202311832510A CN117477049A CN 117477049 A CN117477049 A CN 117477049A CN 202311832510 A CN202311832510 A CN 202311832510A CN 117477049 A CN117477049 A CN 117477049A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
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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
- H01M10/058—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
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/78—Shapes other than plane or cylindrical, e.g. helical
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/30—Arrangements for facilitating escape of gases
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/30—Arrangements for facilitating escape of gases
- H01M50/35—Gas exhaust passages comprising elongated, tortuous or labyrinth-shaped exhaust passages
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a battery capable of absorbing and dredging gas and a battery core comprising the battery, and belongs to the technical field of secondary batteries. The battery comprises a positive electrode current collector, a positive electrode active layer, a diaphragm, a negative electrode active layer, a conductive porous material layer, a negative electrode current collector and electrolyte which are sequentially stacked; the negative electrode current collector is close to one side surface of the conductive porous material layer and is provided with a plurality of grooves with two open ends. The battery cell comprises a battery cell main body and a shell for accommodating the battery cell main body; the battery cell main body comprises a plurality of batteries; the shell is provided with an exhaust port. The battery and the battery core provided by the invention have the functions of adsorbing and guiding out the gas, can effectively solve the problem of gas accumulation in the battery core, and are beneficial to improving the cycle performance and the safety performance of the battery.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a battery capable of absorbing and dredging gas and a battery cell containing the battery.
Background
Fossil energy has the disadvantages of non-renewable and serious pollution, and the problems of resource shortage, ecological environment deterioration and the like are inevitably faced in the world after the uninterrupted exploitation and consumption for hundreds of years. In order to cope with such a situation, new energy technologies such as wind energy and solar energy are increasingly paid attention to. However, because these natural resources are affected by weather, season, altitude, latitude and other conditions, there are regional, intermittent and unstable problems, and the generated electric energy can cause the disorder of the power grid system and can not be directly connected to the grid, so that the difficulty in utilizing clean energy is greatly increased, and the wind and light abandoning is serious. In order to promote efficient utilization of new energy, development of inexpensive and stable large-scale energy storage technologies as a hub for renewable energy storage and conversion has been urgent.
Among the various candidates, electrochemical energy storage has the advantages of low carbon, high conversion efficiency, flexible application and the like, can show diversification in different application scenes, and is the development direction with the highest potential. Since the 70 th century of the 20 th century, the invention has been paid great attention to, and has been developed rapidly, and various types of secondary batteries with high energy, high power and the like have been developed, and are widely used as power sources for vehicles and portable electronic products, and have the potential for large megawatt energy storage power stations.
However, with the prolonged use time, particularly when the secondary battery is subjected to normal temperature charge-discharge cycle for a long time, even when the secondary battery is subjected to high temperature cycle and high temperature storage, gas is generated in the battery, and the generated gas components are related to the positive electrode, the negative electrode and the electrolyte of the battery. On one hand, the gas is generated in the formation and the later charge and discharge processes, and the gas component is CO when the negative electrode SEI film is formed 2 ，C 2 H 4 Etc.; on the other hand, in the circulating and storing process, the electrolyte is oxidized on the surface of the positive electrode, and the alkyl electrolyte salt and the solvent are subjected to oxidative decomposition to generate gas. With the accumulation of generated gas, the battery can bulge, so that the cycle attenuation is accelerated, and the safety problems of battery leakage, explosion, fire and the like are caused. Therefore, how to solve the accumulation of gas, reduce the total amount of gas in the battery cell, and have important significance for promoting the industrialization process of the battery, improving the safety and prolonging the service life of the battery.
CN112615050a discloses a low-gas-production long-circulation high-voltage electrolyte, a preparation method and a lithium ion battery, wherein the main components of the low-gas-production long-circulation high-voltage electrolyte are lithium salt, a solvent and an additive, and the additive comprises one or a combination of more than two additives selected from sodium salt additives, carbonate additives and sulfate additives. The electrolyte is matched with the high-voltage positive electrode, so that the interface of the positive electrode can be protected, the oxidation reaction between the electrolyte and the electrolyte is prevented, gas production is inhibited, and the gas production is reduced.
CN112271341a discloses a laminated battery core and a lithium ion battery, the laminated battery core comprises a negative plate, a diaphragm and a positive plate which are sequentially laminated, a coating is coated on the surface of at least one of the negative plate and the positive plate, and the coating can absorb gas. The surface of at least one pole piece in the laminated battery core is coated with the coating, and the coating can absorb gas, so that on one hand, the gas generated by the battery core of the lithium ion battery during use and thermal runaway can be absorbed, and the safety performance of the lithium ion battery core is improved; on the other hand, the coating is utilized to absorb the gas generated during formation of the lithium ion battery, so that the use amount of the soft package battery aluminum plastic film air bag can be reduced, and the manufacturing cost of the battery core is reduced.
CN113991201a discloses a gas adsorption membrane, a preparation method thereof and a lithium ion battery, the gas adsorption membrane comprises: a separator base layer; at least one side of the membrane base layer is applied with a gas adsorption layer. The gas generated in the circulation and storage processes of the battery is adsorbed by the gas adsorption layer applied to the diaphragm base layer, so that the gas expansion phenomenon of the battery is improved on the premise of little influence on the power of the battery; due to the layered arrangement, the specific surface area is large, the area for absorbing gas is large, and the gas absorbing capacity is better than that of arranging a gas adsorbate in an electrode or electrolyte.
At present, the solution to the problem of gas accumulation in batteries is focused on the aspects of gas production inhibition and gas absorption. While suppressing gas production can reduce gas production, the accumulation of gas in the cell gradually increases over time; the absorption capacity of the absorption layer is limited, and the effect of the absorption layer on a cell with a large amount of generated gas is not obvious.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a battery capable of absorbing and dredging gas and a battery cell comprising the battery. The battery and the battery core have the functions of adsorbing and guiding out gas, can effectively solve the problem of gas accumulation in the battery core, and are beneficial to improving the cycle performance and the safety performance of the battery.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a battery for absorbing and channeling a gas, the battery comprising a positive electrode current collector, a positive electrode active layer, a separator, a negative electrode active layer, a conductive porous material layer, and a negative electrode current collector, which are sequentially stacked, and an electrolyte;
the negative electrode current collector is close to one side surface of the conductive porous material layer and is provided with a plurality of grooves with two open ends.
In the present invention, the term "two-end opening" means that the groove penetrates through the side end surface of the negative electrode current collector, so that two ends of the groove are communicated with the outside of the negative electrode current collector.
In the battery provided by the invention, the conductive porous material layer has large specific surface area, an open pore structure and large pore volume, and can realize selective adsorption and separation of gas molecules with different sizes and different molecular structures; meanwhile, the conductive porous material has excellent conductivity, does not influence the electronic conduction of the negative electrode current collector and the negative electrode active layer, and can adsorb gas and simultaneously maintain a high-speed path for electronic transmission; the grooves on the surface of the negative electrode current collector can provide channels for gas guiding out, so that disordered gas generated on the negative electrode side is effectively discharged out of the cell main body. The invention adopts the thought of becoming sparse, and the whole battery has the functions of absorbing and guiding out gas, so that the problem of gas accumulation in the battery can be effectively solved, and the cycle performance and the safety performance of the battery can be improved.
In the present invention, the method for forming the groove on the surface of the negative electrode current collector is not particularly limited, and may be, for example, electrochemical deposition, nano template method, plasma etching, MOF induced synthesis, micro-nozzle 3D dispensing, etc.
In the present invention, the arrangement manner of the surface grooves of the negative electrode current collector is not particularly limited. For ease of fabrication, the grooves may be all parallel to each other, or some may be parallel to each other in a first direction and some may be parallel to each other in a second direction, with the grooves intersecting each other in both directions.
The parallel direction of the grooves can be any direction in the plane of the negative current collector, for example, the long side direction or the short side direction of the negative current collector, and in this case, a plurality of grooves are parallel to the short side of the negative current collector; or parallel to the long side of the negative current collector; or a part of the negative electrode current collector is parallel to the short side of the negative electrode current collector, and the other part of the negative electrode current collector is parallel to the long side of the negative electrode current collector.
It should be noted that, the parallel direction of the grooves on the surface of the negative current collector needs to be reasonably selected according to the size of the battery. For example, for the lamination cell, the length difference between the long side and the short side of the battery is not large, and the groove is parallel to the short side or the long side of the negative current collector; for the battery core of the winding structure, the length of the long side of the battery is larger, if the grooves are parallel to the long side of the negative electrode current collector, the gas channel is too long, and the gas in the middle of the battery is not beneficial to be led out, at this time, the grooves are preferably arranged to be parallel to the short side of the negative electrode current collector, or one part of the grooves are parallel to the short side of the negative electrode current collector, and the other part of the grooves are parallel to the long side of the negative electrode current collector.
In some embodiments of the invention, the width of the trench is 0.2-1 μm; for example, it may be 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1 μm.
In some embodiments of the invention, the depth of the trench is 50-500 a nm a; for example, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 120 nm, 150 nm, 180 nm, 200 nm, 220 nm, 250 nm, 280 nm, 300 nm, 320 nm, 350 nm, 380 nm, 400 nm, 420 nm, 450 nm, 480 nm, 500 nm, or the like.
In some embodiments of the invention, the spacing between two adjacent grooves is 0.5-5 μm; for example, it may be 0.5 μm, 0.8 μm, 1 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm.
The width, depth and spacing of the grooves on the surface of the negative electrode current collector are set in the ranges, so that the negative electrode current collector has good guiding effect on gas.
In some embodiments of the present invention, a surface of the negative electrode current collector, which is close to the conductive porous material layer, is modified with an aerophilic hydrophobic group.
According to the invention, the hydrophilic and hydrophobic groups are modified on the surface of the negative current collector, so that disordered gas generated on the negative side is attracted into the grooves on the surface of the negative current collector under the action of surface tension, and then the disordered gas is discharged out of the battery core main body, and the air suction and guide functions of the battery are further improved.
The "gas-philic" refers to the gas generated during formation, circulation, and standing, etc., in the battery, such as hydrogen, carbon dioxide, and C 2 H 4 Etc. The kind of the aerophilic hydrophobic group is not particularly limited in the present invention, and may be exemplified by alkyl, fluoroalkyl, etc.
The method for modifying the hydrophilic and hydrophobic groups on the surface of the negative electrode current collector is not particularly limited, and can be exemplified by plasma treatment, surface polymerization and the like.
In some embodiments of the invention, the layer of electrically conductive porous material has a thickness of 1-5 μm; for example, it may be 1.2 μm, 1.5 μm, 1.8 μm, 2 μm, 2.2 μm, 2.5 μm, 2.8 μm, 3 μm, 3.2 μm, 3.5 μm, 3.8 μm, 4 μm, 4.2 μm, 4.5 μm, 4.8 μm or 5 μm.
In some embodiments of the invention, the electrically conductive porous material in the layer of electrically conductive porous material is selected from one or more of electrically conductive porous carbon materials, electrically conductive metal organic frameworks (electrically conductive MOFs). Wherein the conductive porous carbon material includes, but is not limited to, superconducting activated carbon, superconducting carbon black, disordered porous carbon, mesoporous carbon nanofibers, and the like.
In some embodiments of the invention, the conductive porous material in the conductive porous material layer has a specific surface area of 300-3000 m 2 /g; for example 300 m 2 /g、400 m 2 /g、500 m 2 /g、600 m 2 /g、700 m 2 /g、800 m 2 /g、900 m 2 /g、1000 m 2 /g、1200 m 2 /g、1500 m 2 /g、1800 m 2 /g、2000 m 2 /g、2200 m 2 /g、2500 m 2 /g、2800 m 2 /g or 3000 m 2 /g, etc.
In some embodiments of the invention, the separator is a fibrous membrane, and the fibrous surface of the separator has nanochannels.
According to the invention, the nano grooves are formed on the fiber surface of the diaphragm, so that disordered gas generated in the middle part of the battery in the formation and later circulation and shelving processes can be collected and conveyed to the outside of the battery core main body, thus the accumulation of gas in the battery is further reduced, and the circulation performance and the safety performance of the battery are improved.
In the present invention, the method of forming the nano-grooves on the fiber surface of the separator is not particularly limited, and exemplary, the nano-grooves may be constructed by a template sacrificial method. DMF using, for example, PAA (polyamic acid) and PS (polystyrene)N,N-dimethylformamide), and then subjecting the fiber film to high temperature (350 ℃) at which time the PAA undergoes cyclization reaction to form PI (polyimide) and the PS is decomposed, thereby forming nano-grooves on the surface of the fiber.
In some embodiments of the present invention, the separator is made of polyimide, polypropylene or polyethylene.
In some embodiments of the invention, the membrane surface is modified with an aerophilic hydrophobic group. The type, action and formation method of the aerophilic hydrophobic group on the surface of the diaphragm are the same as those of the aerophilic hydrophobic group on the surface of the negative current collector.
In the present invention, the materials of the positive electrode current collector and the negative electrode current collector are not particularly limited, and exemplary metals that do not undergo alloying reaction with the active metal of the battery include, but are not limited to, copper, aluminum, nickel, stainless steel, titanium, cobalt, iron, etc.; preferably, the positive current collector is aluminum foil, and the negative current collector is copper foil. Wherein, the active metal of the battery refers to the metal participating in electrode reaction in the battery. For example, for lithium ion batteries, the active metal is lithium; for sodium ion batteries, the active metal is sodium.
In the present invention, the positive electrode active layer and the negative electrode active layer refer to film layers containing a positive electrode active material and a negative electrode active material, respectively. Typically, the layer contains a binder and/or a conductive agent in addition to the active material. The invention is not particularly limited in the kind of the positive electrode active material, the negative electrode active material, and for sodium ion batteries, the positive electrode active material includes, but is not limited to, layered materials, polyanion materials, prussian blue/white compounds, and the like; the negative active material includes, but is not limited to, one or more of hard carbon, soft carbon, modified hard carbon, graphite.
In some embodiments of the invention, the battery further comprises a positive electrode tab connected to the positive electrode current collector, and a negative electrode tab connected to the negative electrode current collector.
In some embodiments of the invention, the battery is a sodium ion battery, a lithium ion battery, a potassium ion battery, a zinc ion battery, or a magnesium ion battery.
In a second aspect, the present invention provides a cell for absorbing and channeling a gas, the cell comprising a cell body and a housing containing the cell body;
the cell body comprising a plurality of cells as described in the first aspect; the shell is provided with an exhaust port.
According to the invention, the exhaust port is arranged on the battery cell shell and combined with the battery structure in the first aspect, so that the gas can be rapidly and comprehensively exhausted out of the battery cell by using an external air exhaust system.
In the invention, the exhaust port is a switchable exhaust port which is opened only when the air is exhausted, and is closed when the air is not exhausted, so that external air is prevented from entering the battery cell. For the soft package battery core, the exhaust port can be in the form of a heat-sealing PP pipe and a rubber plug; for hard-shell cells, the vent may be in the form of a vent valve.
In some embodiments of the invention, a plurality of the cells are in a laminated or wound configuration.
Compared with the prior art, the invention has the following beneficial effects:
in the battery provided by the invention, the conductive porous material layer has large specific surface area, an open pore structure and large pore volume, and can realize selective adsorption and separation of gas molecules with different sizes and different molecular structures; meanwhile, the conductive porous material has excellent conductivity, does not influence the electronic conduction of the negative electrode current collector and the negative electrode active layer, and can adsorb gas and simultaneously maintain a high-speed path for electronic transmission; the grooves on the surface of the negative electrode current collector can provide channels for gas guiding out, so that disordered gas generated on the negative electrode side is effectively discharged out of the cell main body; by further forming nano grooves on the fiber surface of the diaphragm and modifying the hydrophilic and hydrophobic groups on the surfaces of the diaphragm and the negative electrode current collector, the air suction and guide functions of the battery can be further improved. The invention adopts the thought of becoming sparse, and the whole battery has the functions of absorbing and guiding out gas, so that the problem of gas accumulation in the battery can be effectively solved, and the cycle performance and the safety performance of the battery can be improved.
Drawings
Fig. 1 is a schematic structural diagram of a battery according to an embodiment of the present invention;
fig. 2 is a schematic surface structure of a negative current collector in a battery according to embodiment 1 of the present invention;
fig. 3 is a schematic side view of a negative current collector in the battery according to embodiment 1 of the present invention;
fig. 4 is a schematic surface structure of a negative current collector in a battery according to embodiment 2 of the present invention;
fig. 5 is a graph showing the capacity retention ratio of the battery provided by the examples of the present invention and the comparative examples; wherein, the reference numerals are as follows: 10-positive electrode current collector, 20-positive electrode active layer, 30-separator, 40-negative electrode active layer, 50-conductive porous material layer and 60-current collector.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. It should be apparent to those skilled in the art that the detailed description is merely provided to aid in understanding the invention and should not be taken as limiting the invention in any way.
Example 1
The present embodiments provide a battery and a cell that absorbs and channels gas;
the structure of the battery is shown in fig. 1, and comprises a positive electrode current collector 10, a positive electrode active layer 20, a diaphragm 30, a negative electrode active layer 40, a conductive porous material layer 50, a negative electrode current collector 60 and an electrolyte which are sequentially stacked; positive electrode tab (not shown) is connected to positive electrode current collector 10, and negative electrode tab (not shown) is connected to negative electrode current collector 60;
the structure of the negative current collector 60 is as shown in fig. 2 and 3, the surface of the negative current collector 60 is provided with a plurality of grooves with two open ends, the grooves are parallel to the short sides of the negative current collector 60, the width of each groove is 1 μm, the depth of each groove is 300 nm, and the interval between every two adjacent grooves is 3 μm; a surface of one side of the negative electrode current collector 60, which is close to the conductive porous material layer 50, is modified with an aerophilic hydrophobic group;
the diaphragm 30 is a fibrous membrane, the surface of the fiber of the diaphragm is provided with nano grooves, and the surface of the diaphragm 30 is modified with an aerophilic hydrophobic group;
the battery cell comprises a battery cell main body and a shell for accommodating the battery cell main body; the battery cell main body comprises a plurality of batteries provided by the embodiment of the lamination structure, and the shell is provided with an exhaust port.
The preparation method of the battery and the battery core for absorbing and dredging the gas provided by the embodiment is as follows:
(1) Adding an anode active material NVP (sodium vanadium phosphate), a conductive agent SP and a binder PVDF (polyvinylidene fluoride) into a solvent NMP (N-methylpyrrolidone) according to the mass ratio of 94:3:3, and uniformly stirring to prepare anode slurry;
coating positive electrode slurry on two sides of the surface of an aluminum foil (positive electrode current collector, thickness of 12 mu m), and drying, rolling and slitting in an oven to prepare a positive electrode plate, wherein the thickness of a positive electrode active layer is 45 mu m;
(2) Etching the grooves on the two sides of a copper foil (a negative current collector with the thickness of 8 mu m) by adopting a plasma etching technology;
using Plasma vacuum Plasma processor to process the copper foil with groove etched on the surface under the condition of 24W power, 24 hydrogen and carbon dioxide as gas medium, to graft-CH on the copper foil surface 2 CH 3 ；
(3) Super conductive carbon black (available from Cabot Corp., specific surface area 1500 m) 2 And/g) coating the two sides of the copper foil obtained in the step (2) by adopting a dry spraying process to form a conductive porous material layer, wherein the thickness of the conductive porous material layer is 1 mu m;
adding hard carbon (purchased from Kuraray company), a conductive agent SP and a binder PVDF (polyvinylidene fluoride) into a solvent NMP (N-methylpyrrolidone) in a mass ratio of 95:2:3, and uniformly stirring to prepare negative electrode slurry;
coating the negative electrode slurry on the surface of the conductive porous material layer, and drying in an oven, rolling and slitting to obtain a negative electrode plate, wherein the thickness of the negative electrode active layer is 55 mu m;
(4) Adopting a sacrificial template method, dissolving polyamide acid (purchased from Kemike company, PAA) and PS (PS) with a mass ratio of 1:2 in DMF (total concentration of 10 wt%) and adopting an electrostatic spinning method after uniformly stirring at a high speed to prepare a fiber membrane in a high-voltage electrostatic spinning system of 18kV, and then placing the fiber membrane at a high temperature (350 ℃) of 1 h to obtain a membrane with a nano groove structure, wherein the fiber diameter is 200-500 nm, the membrane porosity is 40%, and the thickness is 30 mu m;
using Plasma vacuum Plasma processor to process the surface of diaphragm at low temperature under the condition of 24W power and 24 hydrogen as gas medium to separateMembrane surface grafting-CH 2 CH 3 ；
(5) Separating the positive plate and the negative plate by using a diaphragm, arranging the positive plate and the negative plate according to a rule, and stacking for a plurality of times, wherein the outermost two layers are negative current collectors, and the outer surfaces of the two layers are of a plane structure;
(6) Connecting a positive electrode tab on a positive electrode current collector, connecting a negative electrode tab on a negative electrode current collector, and then placing the battery cell in a 65 ℃ vacuum oven for baking for 24 hours to obtain a battery cell main body without electrolyte;
(7) Packaging the cell main body without electrolyte (reserving a switchable exhaust port on the surface), and injecting liquid (the electrolyte is NaPF-containing) 6 Purchased from SmoothWay corporation), sealed, formed, aged and volumetric to obtain the cell of the laminated structure that absorbs and channels the gas.
Example 2
The present embodiments provide a battery and a cell that absorbs and channels gas;
the structure of the battery is shown in fig. 1, and comprises a positive electrode current collector 10, a positive electrode active layer 20, a diaphragm 30, a negative electrode active layer 40, a conductive porous material layer 50, a negative electrode current collector 60 and an electrolyte which are sequentially stacked; positive electrode tab (not shown) is connected to positive electrode current collector 10, and negative electrode tab (not shown) is connected to negative electrode current collector 60;
the structure of the negative electrode current collector 60 is shown in fig. 4, wherein the surface of the negative electrode current collector 60 is provided with a plurality of grooves with two open ends, one part of the grooves is parallel to the short side of the negative electrode current collector 60, the other part of the grooves is parallel to the long side of the negative electrode current collector 60, the width of the grooves is 0.5 μm, the depth is 100 nm, and the interval between two adjacent parallel grooves is 2 μm; a surface of one side of the negative electrode current collector 60, which is close to the conductive porous material layer 50, is modified with an aerophilic hydrophobic group;
the diaphragm 30 is a fibrous membrane, the surface of the fiber of the diaphragm is provided with nano grooves, and the surface of the diaphragm 30 is modified with an aerophilic hydrophobic group;
the battery cell comprises a battery cell main body and a shell for accommodating the battery cell main body; the battery cell main body comprises a plurality of batteries provided by the embodiment of the winding structure, and the shell is provided with an exhaust port.
The preparation method of the battery and the battery core for absorbing and dredging the gas provided by the embodiment is as follows:
(1) Adding an anode active material NVP (sodium vanadium phosphate), a conductive agent SP and a binder PVDF (polyvinylidene fluoride) into a solvent NMP (N-methylpyrrolidone) according to the mass ratio of 94:3:3, and uniformly stirring to prepare anode slurry;
coating positive electrode slurry on two sides of the surface of an aluminum foil (positive electrode current collector, thickness of 12 mu m), and drying, rolling and slitting in an oven to prepare a positive electrode plate, wherein the thickness of a positive electrode active layer is 45 mu m;
(2) Etching the grooves on the two sides of a copper foil (a negative current collector with the thickness of 8 mu m) by adopting a plasma etching technology;
using Plasma vacuum Plasma processor to process the copper foil with groove etched on the surface under the condition of 24W power and 24 carbon tetrafluoride as gas medium, so as to graft-CF on the surface of the copper foil 2 CF 3 ；
(3) Super conductive carbon black (available from Cabot Corp., specific surface area 1500 m) 2 And/g) coating the two sides of the copper foil obtained in the step (2) by adopting a dry spraying process to form a conductive porous material layer, wherein the thickness of the conductive porous material layer is 1 mu m;
adding a negative electrode active material hard carbon (purchased from Kuraray company), a conductive agent SP and a binder PVDF into a solvent NMP according to the mass ratio of 95:2:3, and uniformly stirring to prepare a negative electrode slurry;
coating the negative electrode slurry on the surface of the conductive porous material layer, and drying in an oven, rolling and slitting to obtain a negative electrode plate, wherein the thickness of the negative electrode active layer is 50 mu m;
(4) Adopting a sacrificial template method, dissolving polyamide acid (purchased from Kemike company, PAA) and PS with a mass ratio of 1:1.5 in DMF (total concentration of 10 wt%) and adopting an electrostatic spinning method after uniformly stirring at a high speed to prepare a fiber membrane in a high-voltage electrostatic spinning system of 18kV, and then placing the fiber membrane at a high temperature (350 ℃) of 1 h to obtain a membrane with a nano groove structure, wherein the fiber diameter is 200-500 nm, the membrane porosity is 36%, and the thickness is 30 mu m;
using Plasma vacuum Plasma processor to process the surface of diaphragm with low temperature Plasma under the condition of 24W power and 24 carbon tetrafluoride as gas medium to graft-CF on the surface of diaphragm 2 CF 3 ；
(5) Laminating four layers of the positive plate, the diaphragm, the negative plate and the diaphragm together, and then winding;
(6) Connecting a positive electrode tab on a positive electrode current collector, connecting a negative electrode tab on a negative electrode current collector, and then placing the battery cell in a 65 ℃ vacuum oven for baking for 24 hours to obtain a battery cell main body without electrolyte;
(7) Packaging the cell main body without electrolyte (reserving a switchable exhaust port on the surface), and injecting liquid (the electrolyte is NaPF-containing) 6 Purchased from SmoothWay corporation), sealed, formed, aged and volumetric to obtain the wound structure of the cell that absorbs and channels the gas.
Example 3
This example provides a battery and cell that absorbs and channels gas, differing from example 1 only in that the surfaces of separator 30 and negative current collector 60 are not modified with a gas-philic hydrophobic group.
Example 4
This example provides a battery and a cell that absorb and channel gas, differing from example 1 only in that a PAA solution having a concentration of 10wt% was directly used in step (4) to prepare a PI fiber film as the separator 30 by electrospinning under the same conditions.
Comparative example 1
This comparative example provides a battery and cell differing from example 4 only in that the conductive porous material layer 50 is absent.
Comparative example 2
This comparative example provides a battery and a cell differing from example 4 only in that the conductive porous material layer 50 is not contained and the surface of the negative electrode current collector 60 is flat.
Performance testing
The electrochemical performance of the gas-absorbing and gas-channeling cells provided in the above examples and comparative examples was tested as follows:
cyclic stability: in the environment of 25 ℃, constant-current charge and discharge circulation is carried out by using 1C (1A) current, the voltage interval is 2.0-3.65V, and the circulation is carried out for 50 circles. Nth turn capacity retention = nth turn discharge capacity/first turn discharge capacity.
The cycle capacity retention ratio comparison charts of the above examples and comparative examples are shown in fig. 5, and the 50 th cycle capacity retention ratio data are shown in table 1 below.
TABLE 1
As can be seen from the test results of fig. 5 and table 1, the gas-absorbing and-conducting battery provided by the present invention has good cycle stability because the gas generated in the battery can be discharged out of the battery cell main body.
Among them, in example 3, since the surface of the separator and the negative electrode current collector is not modified with the hydrophilic and hydrophobic groups, and in example 4, since the general PI fiber film having no nano grooves and not modified with the hydrophilic and hydrophobic groups is used as the separator, its ability to absorb and channel gas is lowered, and thus the circulation stability is lowered.
Compared with example 4, comparative example 1 did not contain a conductive porous material layer, and comparative example 2 did not contain a conductive porous material layer and the surface of the negative electrode current collector was flat, and its ability to absorb and channel gas was greatly reduced, so that the cycle stability was significantly deteriorated.
The foregoing is merely a specific embodiment of the disclosure to enable one skilled in the art to understand or practice the disclosure. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown and described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A battery for absorbing and dredging gas, characterized in that the battery comprises a positive electrode current collector, a positive electrode active layer, a diaphragm, a negative electrode active layer, a conductive porous material layer, a negative electrode current collector and an electrolyte which are sequentially stacked;
the negative electrode current collector is close to one side surface of the conductive porous material layer and is provided with a plurality of grooves with two open ends.
2. The battery of claim 1, wherein a plurality of the grooves are parallel to a short side of the negative current collector; or parallel to the long side of the negative current collector; or a part of the negative electrode current collector is parallel to the short side of the negative electrode current collector, and the other part of the negative electrode current collector is parallel to the long side of the negative electrode current collector.
3. The cell of claim 1, wherein the width of the trench is 0.2-1 μιη;
and/or the depth of the groove is 50-500 nm;
and/or the interval between two adjacent grooves is 0.5-5 μm.
4. The battery according to claim 1, wherein a surface of a side of the negative electrode current collector adjacent to the conductive porous material layer is modified with an aerophilic hydrophobic group.
5. The battery of any one of claims 1-4, wherein the layer of electrically conductive porous material has a thickness of 1-5 μιη;
and/or the conductive porous material in the conductive porous material layer is selected from one or more of conductive porous carbon material and conductive metal organic frame;
and/or the specific surface area of the conductive porous material in the conductive porous material layer is 300-3000 m 2 /g。
6. The battery of any one of claims 1-4, wherein the separator is a fibrous membrane, the fibrous surface of the separator having nanochannels;
and/or the material of the diaphragm is polyimide, polypropylene or polyethylene;
and/or the surface of the diaphragm is modified with an aerophilic hydrophobic group.
7. The battery of any one of claims 1-4, further comprising a positive tab connected to the positive current collector and a negative tab connected to the negative current collector.
8. The battery of any one of claims 1-4, wherein the battery is a sodium ion battery, a lithium ion battery, a potassium ion battery, a zinc ion battery, or a magnesium ion battery.
9. A cell for absorbing and channeling a gas, the cell comprising a cell body and a housing for receiving the cell body;
the cell body comprising a plurality of cells as defined in any one of claims 1-8; the shell is provided with an exhaust port.
10. The cell of claim 9, wherein a plurality of the cells are in a laminated or wound configuration.
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