CN113889711A - Metal composite membrane capable of adsorbing gas, preparation method thereof and bagged battery - Google Patents
Metal composite membrane capable of adsorbing gas, preparation method thereof and bagged battery Download PDFInfo
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- CN113889711A CN113889711A CN202111049500.0A CN202111049500A CN113889711A CN 113889711 A CN113889711 A CN 113889711A CN 202111049500 A CN202111049500 A CN 202111049500A CN 113889711 A CN113889711 A CN 113889711A
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- activated carbon
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- aluminum
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Images
Classifications
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/1243—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the internal coating on the casing
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention relates to the technical field of aluminum-plastic films, and particularly discloses a metal composite film capable of adsorbing gas, which consists of an aluminum-plastic film, an active carbon adsorption layer and a selective permeation film; the active carbon adsorption layer is arranged on the inner side of the aluminum-plastic film, which is in contact with the electrolyte when the aluminum-plastic film is used for packaging the battery; the active carbon adsorption layer is covered with a selective permeation membrane with the area larger than that of the active carbon adsorption layer. The method is characterized in that a layer of activated carbon slurry with high specific surface area and developed pore size distribution is coated on the inner side which is contacted with electrolyte when the aluminum plastic film is used for packaging the battery, so that excessive C in an electrochemical system is adsorbed2H4With CO2Gas, thereby solving the problem of excessive gas generation of the battery in the battery core to controlThe internal pressure of the battery is controlled, and the safety problem caused by the overhigh internal pressure of the battery is effectively avoided.
Description
Technical Field
The invention relates to the technical field of aluminum-plastic films, in particular to a metal composite film capable of adsorbing gas, a preparation method thereof and a bagged battery.
Background
With the increasing demand of people for new energy automobiles and various 3C digital products, lithium ion secondary batteries with high energy density are continuously developed and applied to various fields. However, under abnormal use conditions such as storage, circulation, overcharge and overdischarge of the lithium ion secondary battery in a high temperature environment, the electrolyte is easily decomposed to generate gas, and the gas is accumulated in the battery cell to cause an increase in internal pressure of the battery cell, which brings about a series of problems. Firstly, bubbles can be formed on a contact interface of the electrolyte and an electrode and a diaphragm, and the bubbles can influence the diffusion and transmission of lithium ions, so that the internal resistance of the battery cell is increased, and the electrochemical performance of the battery cell is influenced; secondly, the electrode may be deformed due to overhigh internal pressure, and the risk of short circuit in the battery cell is increased; the high pressure gas can also deform the cell casing, which can lead to fire or explosion.
Lithium ion secondary batteries produce mainly N2，C2H6，C2H4，CO2，CO，H2Equal gasThe most abundant is C2H4With CO2Gas, C2H4The main source of the gas is the decomposition of an EC solvent in the electrolyte on the surface of a negative electrode to form an SEI film and the reformation caused by the broken SEI film; CO 22It is derived from the oxidative decomposition of the alkyl lithium carbonate and the solvent.
The problem of gas generation of the battery is not solved by the conventional bagged battery technology in a simple and economic way, and a safety valve is usually arranged on an aluminum plastic film of the bagged battery and is connected with the aluminum plastic film through hot melt adhesive. Because the limit pressure that bagged battery and relief valve ball/valve block bore is different, when the gas reaches the relief valve pressure value in the bag, the relief valve is opened, discharges inside gas to the outside, reaches the purpose that prevents the lithium cell and cause the battery security problem because inside atmospheric pressure is too big. However, the safety valve is mostly composed of a compression spring, a metal ball or a metal sheet and a valve shell, and has the problems of complex structure, difficult installation and the like; or the elastic metal alloy with different deformation and the valve shell are formed, although the structure is superior to that of a compression spring safety valve, the metal alloy has high manufacturing cost, and the hot melt adhesive is also required to be connected with the aluminum plastic film, so that the problem of difficult installation exists. In addition, once the safety valve is opened, the internal environment is connected with the external environment, so that the battery is judged to be invalid, and meanwhile, alkane, ether and olefin combustible gases in the battery are directly discharged to the environment, so that environmental pollution and potential safety hazards are caused.
At present, another method is to solve the problem of gas generation from the inside of the battery, and an MH alloy substance is added to prepare an electrode capable of adsorbing gas during the preparation of the electrode, so that the generated gas is adsorbed in crystal lattices by an alloy material mixed in the electrode during the operation of the battery, and the purpose of inhibiting the gas generation expansion of the battery is achieved. However, MH metal is expensive to manufacture, can only adsorb hydrogen, and has high requirements for the process, which makes large-scale popularization difficult.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention starts from the aluminum plastic film of the soft package battery, and a layer of porous hair with high specific surface area and diameter distribution is sprayed or brushed on the inner side of the aluminum plastic film corresponding to the position of a naked electric coreActivated carbon material for adsorbing excessive C in electrochemical system2H4With CO2Gas, thereby solving the problem of excessive gas generation of the battery in the battery core so as to control the internal pressure of the battery and effectively avoid the safety problem caused by the overhigh internal pressure of the battery. Meanwhile, the attenuation is inhibited, the electrochemical performance of the lithium battery is improved, and the service life of the lithium battery is prolonged.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the invention aims to provide a metal composite membrane capable of adsorbing gas, which consists of an aluminum plastic membrane, an activated carbon adsorption layer and a selective permeation membrane; the active carbon adsorption layer is arranged on the inner side (which can be briefly described as the inner side of the aluminum-plastic film) which is in contact with the electrolyte when the aluminum-plastic film is used for packaging the battery; the active carbon adsorption layer is covered with a selective permeation membrane with the area larger than that of the active carbon adsorption layer.
Further, the activated carbon adsorption layer is formed by coating and drying activated carbon slurry; the active carbon slurry comprises an active carbon material, an adhesive and a solvent.
Furthermore, the solid content of the activated carbon slurry is 55-65%, wherein the solid content is 92-95 parts by weight of the activated carbon material and 5-8 parts by weight of the adhesive.
Specifically, the activated carbon material has a three-dimensional hierarchical porous structure with micropores, mesopores and macropores; the particle size distribution is 1.40-2.90 μm for D10, 4.20-6.40 μm for D50, and 8.20-14.10 μm for D90.
Preferably, the particle size distribution of the activated carbon material is D10: 1.47-2.82 μm, D50: 4.23-6.33 μm and D90: 8.21-14.05 μm.
Specifically, the specific surface area of the activated carbon material is 1600m2/g～2100m2/g。
Preferably, the specific surface area of the activated carbon material is 1689m2/g～2100m2/g。
Specifically, the adhesive is at least one of polytetrafluoroethylene, vinylidene fluoride, styrene butadiene rubber, polyvinyl alcohol, polyethylene and polypropylene.
Further, the material of the selective permeation membrane is selected from one of polytetrafluoroethylene, vinylidene fluoride and nylon 6.
The invention aims to further provide a preparation method of the gas-adsorbable metal composite membrane, which comprises the following steps:
(1) preparing activated carbon slurry:
mixing an activated carbon material, an adhesive and a solvent, and uniformly stirring to obtain the activated carbon slurry; the solid content of the activated carbon slurry is 55-65%, wherein the solid content is 92-95 parts by weight of an activated carbon material and 5-8 parts by weight of an adhesive;
(2) and (3) forming an activated carbon adsorption layer:
uniformly coating the prepared activated carbon slurry on the inner side of the aluminum-plastic film, which is in contact with the electrolyte when the aluminum-plastic film is used for packaging the battery, and drying to form an activated carbon adsorption layer;
(3) preparing the gas-adsorbable metal composite membrane:
and then covering a selective permeation film with the area larger than that of the activated carbon adsorption layer on the activated carbon adsorption layer, wherein the selective permeation film is fixed on the inner side of the aluminum plastic film, which is in contact with the electrolyte when the aluminum plastic film is used for packaging the battery, in a thermoplastic mode.
The present invention also provides a pouch-pack battery comprising any one of the above-described gas-adsorbable metal composite films.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention coats a layer of activated carbon slurry with high specific surface area and developed pore size distribution on the inner side contacting with electrolyte when the aluminum plastic film is used for packaging the battery, thereby adsorbing excessive C in an electrochemical system2H4With CO2Gas, so that excessive gas generation of the battery is solved in the battery core to control the internal pressure of the battery, and the safety problem caused by excessive internal pressure of the battery is effectively avoided;
(2) the developed pore size distribution ensures that the volume expansion of the bagged battery is smaller after the adsorption layer adsorbs gas, so that the battery can adsorb a large amount of formed gas in the battery forming period, an air bag is omitted, the step of secondary battery sealing is omitted, the material cost and the labor cost of an aluminum-plastic film are greatly reduced, in addition, the smaller volume expansion of the battery provides great space for the electrochemical design of the battery, and the method is a great progress in the field of power batteries particularly pursuing high specific energy and low cost;
(3) the invention can also improve the electrochemical performance of the battery, inhibit attenuation, prolong the service life of the battery and be used in a high temperature resistant environment.
Drawings
FIG. 1 is a schematic cross-sectional view of a gas-adsorbable metal composite membrane according to the present invention;
FIG. 2 is a schematic structural diagram of a gas-adsorbing metal composite film after a pit flushing process according to the present invention;
FIG. 3 is a scanning electron micrograph of an activated carbon material according to the present invention;
FIG. 4 is a transmission electron micrograph of an activated carbon material of the present invention;
FIG. 5 is a graph showing the adsorption and desorption curves of the specific surface area of the activated carbon material according to the present invention;
FIG. 6 is a graph of pore size distribution for an activated carbon material of the present invention;
FIG. 7 is a graph of pore size range versus pore specific surface area for an activated carbon material of the present invention;
FIG. 8 is a graph of the cycle life of a battery run at 55 ℃ for 1000 cycles of example 3 of the present invention and comparative examples 7, 8, and 9;
description of the element reference numerals
1. Inner side of contact electrolyte when aluminum plastic film is used for packaging battery
2. Activated carbon adsorption layer
3. Permselective membranes
4. Pit punching
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The specific embodiment of the invention provides a metal composite membrane capable of adsorbing gas, which consists of an aluminum plastic membrane, an activated carbon adsorption layer 2 and a selective permeation membrane 3; the active carbon adsorption layer 2 is arranged on the inner side 1 of the aluminum-plastic film which is contacted with electrolyte when the aluminum-plastic film is used for packaging the battery; the activated carbon adsorption layer 2 is covered with a selective permeation membrane 3 with the area larger than that of the activated carbon adsorption layer.
Here, the structure of the aluminum plastic film itself is not limited as long as a person skilled in the art can prepare the aluminum plastic film for a pouch battery. For example, the aluminum plastic film can comprise an outer base material resin layer, an intermediate metal layer, an inner adhesive layer and an inner heat welding layer; and the paint also comprises an anti-corrosion layer, an outer adhesive layer and a coloring layer. When defined as an internal heat sealing layer, the inner side 1 of the aluminium-plastic film according to the invention, which is in contact with the electrolyte when used for packaging a battery, is the side of the aluminium-plastic film where the heat sealing layer is in contact with the electrolyte.
Further, the thickness of the activated carbon adsorption layer 2 is 40-70 μm.
Further, the activated carbon adsorption layer 2 is formed by coating and drying activated carbon slurry; the active carbon slurry comprises an active carbon material, an adhesive and a solvent.
Furthermore, the solid content of the activated carbon slurry is 55-65%, wherein the solid content is 92-95 parts by weight of the activated carbon material and 5-8 parts by weight of the adhesive.
Preferably, the activated carbon material has a three-dimensional hierarchical porous structure with micropores, mesopores and macropores; the particle size distribution is 1.40-2.90 μm for D10, 4.20-6.40 μm for D50, and 8.20-14.10 μm for D90. The particle size distribution of the activated carbon material is more preferably D10: 1.47-2.82 μm, D50: 4.23-6.33 μm and D90: 8.21-14.05 μm.
Preferably, the specific surface area of the activated carbon material is 1600m2/g～2100m2(ii) in terms of/g. It is further preferred that the activated carbon material has a specific surface area of 1689m2/g～2100m2/g。
The developed hierarchical porous structure realizes three-dimensional interpenetration of mesopores on macropores and micropores on the mesopores, pore-forming is carried out on the pores, and developed pore size distribution of the pores in the pores improves the specific surface area of an active material, increases active sites which can be adsorbed by gas, and is beneficial to physical adsorption of gas molecules; in the pore-forming process, the pore-forming agent can form a large amount of oxygen-containing functional groups on the surface of the activated carbon material, which is beneficial to the chemical adsorption of the activated carbon material to gas molecules, and the pore diameter structure and the pore diameter distribution can not cause the larger expansion of the adsorption material after adsorbing gas, thereby avoiding the extrusion of the adsorption layer to the electrode; the particle size distribution is beneficial to coating of the active carbon slurry, so that the surface density of the active carbon of the adsorption layer is the highest.
As shown in fig. 3, as can be seen from a scanning electron microscope image of the activated carbon material, the surface has developed pore diameters, which are mainly shown as macropores; as shown in fig. 4, as can be seen from the transmission electron micrograph, the prepared activated carbon has a three-dimensional interpenetrating structure, and a large number of micropores can be observed on a 5nm scale; as shown in FIGS. 5 to 7, it is shown that the material has more micropores below 2nm, and the number of micropores in the range of 0.5 to 1nm is the largest. Therefore, the combination of a scanning electron microscope and a transmission electron microscope can determine that the activated carbon material of the adsorption layer 2 has a hierarchical porous structure with micropores, mesopores and macropores, and is a good gas adsorption material.
Here, the preparation method of the activated carbon material: adding an activated carbon precursor into an activating agent aqueous solution, stirring at 50 ℃, crosslinking the precursor and the activating agent into gel, then putting the gel into an oven at 80 ℃ for drying for 2h, putting the dried product into a tubular furnace, and carbonizing and activating in an inert gas atmosphere. And after the activation process is finished, when the temperature of the tubular furnace is reduced to room temperature, cleaning the activated product, and then drying to obtain the activated carbon material with the high-specific-surface-area three-dimensional interpenetrating hierarchical porous structure required by the adsorption layer.
In the preparation method of the activated carbon, the activated carbon precursor is one of starch, flour or biomass fiber; the inert gas is one of nitrogen and argon; the activating agent is KOH, NaOH or ZnCl2At least one of NaCl, wherein the ratio of the precursor to the activator is 1-2; in the carbonization and activation process, the temperature rising rate is 5 ℃/min, the temperature rises from room temperature to 400 ℃, and the carbonization and activation process stays at 400 ℃ for 1-2 h; then raising the temperature from 400 ℃ to 800 ℃ at the heating rate of 5 ℃/min, and staying at 800 ℃ for 1h for activationAnd (4) transforming. And when the temperature of the tubular furnace is reduced to room temperature, cleaning the activated product until the solution is neutral, and then drying to obtain the activated carbon material.
Specifically, the adhesive is at least one of polytetrafluoroethylene, vinylidene fluoride, styrene butadiene rubber, polyvinyl alcohol, polyethylene and polypropylene.
Specifically, the solvent is not limited, and may be, for example, acetonitrile, ethyl acetate, ethylene carbonate, cyclohexanone, propylene carbonate, or the like.
Further, the material of the selective permeation membrane 3 is selected from one of polytetrafluoroethylene, vinylidene fluoride and nylon 6.
Furthermore, the selective permeation membrane 3 is fixed on the inner side 1 of the aluminum plastic membrane through a thermoplastic mode, and the activated carbon adsorption layer 2 is prevented from contacting with the electrolyte.
Here, the four sides of the permselective membrane 3 do not exceed the top-side sealing boundary, because the difference in the softening point of the polymer material may affect the sealing performance of the aluminum plastic membrane.
Here, the permselective membrane 3 is gas-impermeable to the electrolyte, and therefore, it is possible to prevent the electrolyte in the battery from being adsorbed by the activated carbon adsorption layer 2, resulting in poor electrochemical performance of the battery and poor gas adsorption performance of the activated carbon adsorption layer 2.
The specific embodiment of the invention also provides a preparation method of the gas-adsorbable metal composite membrane, which comprises the following steps:
(1) preparing activated carbon slurry:
mixing an activated carbon material, an adhesive and a solvent, and uniformly stirring to obtain the activated carbon slurry; the solid content of the activated carbon slurry is 55-65%, wherein the solid content is 92-95 parts by weight of an activated carbon material and 5-8 parts by weight of an adhesive;
(2) formation of activated carbon adsorption layer 2:
uniformly coating the prepared activated carbon slurry on the inner side 1 of the aluminum-plastic film, which is in contact with the electrolyte when the aluminum-plastic film is used for packaging the battery, and drying to form an activated carbon adsorption layer 2;
(3) preparing the gas-adsorbable metal composite membrane:
and then cover a layer of selective permeation membrane 3 that the area is greater than activated carbon adsorption layer 2 on said activated carbon adsorption layer 2, said selective permeation membrane 3 is fixed on the inside 1 that contacts the electrolyte when said plastic-aluminum membrane is used for packing the battery through the thermoplastic form.
Embodiments of the present invention also provide a pouch battery including any one of the above-described gas-adsorbable metal composite films.
Here, in the process of manufacturing the pouch battery, the selection of the materials such as the positive electrode, the negative electrode, the electrolyte, and the like, and the winding or stacking process is not limited as long as the pouch battery can be manufactured, and for example, the pouch battery can be manufactured by selecting the positive electrode nickel cobalt manganese 523(NCM523), the negative electrode graphite, and the winding process.
Here, as shown in fig. 2, the position of the punching pit 4 should coincide with the position of the activated carbon adsorption layer 2 during the punching process, and the activated carbon adsorption layer 2 cannot coincide with the heat-seal area, otherwise the tightness of the top side seal of the battery is affected.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the relevant data were determined as follows:
1. the battery gas volume test method comprises the following steps: and (4) testing by a liquid discharge method, namely suspending the battery cell after gas generation in liquid, and observing the rising volume of the liquid level to obtain the gas generation volume.
2. The gas composition and the ratio were analyzed by gas chromatography.
3. The thickness of the battery core is tested by a flat plate thickness gauge.
4. The K value is tested by a voltage detection device (such as a universal meter, a blue battery, an electrochemical workstation)
5. The specific surface area and the pore size distribution of the activated carbon material are tested by a Michellac ASAP2020 specific surface area tester.
Example 1
The gas-bag-free aluminum-plastic film bagged battery capable of adsorbing gas based on the high-specific-surface-area activated carbon material comprises an adsorption layer 2 coated on an aluminum-plastic film and a selective permeation film 3 positioned between the adsorption layer 2 and a naked electric core;the adsorption layer 2 is 40 μm and is prepared by coating, drying and rolling activated carbon slurry. The solid content of the activated carbon slurry is 55 percent, wherein the specific surface area of the activated carbon is 1689m2(iv)/g, particle size distribution D10:1.47 μm, D50:4.23 μm, D90:8.21 mu m, and 92 parts of activated carbon material in the activated carbon slurry by weight; the adhesive is polytetrafluoroethylene and accounts for 8 parts; the solvent is ethylene carbonate; the selective permeation membrane 3 is a polytetrafluoroethylene membrane.
The battery is composed of a winding bare cell of a positive graphite cathode of the NCM523 and the air-bag-free aluminum plastic film packaging bag containing the adsorption layer 2 and the selective permeation film 3, and the size of the bare cell is 51 × 90 × 3.5 mm. After the prepared battery core is formed by hot pressing at 45 ℃, the thickness of the battery core, the change of the thickness of the battery core before formation and the internal gas production of the bagged battery are observed.
Comparative example 1
The gas-adsorbable aluminum-plastic film bagged battery with the air bag based on the high-specific-surface-area activated carbon material comprises an adsorption layer 2 coated on an aluminum-plastic film; the adsorption layer 2 is 40 μm and is prepared by coating, drying and rolling activated carbon slurry. The solid content of the activated carbon slurry is 55 percent, wherein the specific surface area of the activated carbon is 1689m2(iv)/g, particle size distribution D10:1.47 μm, D50:4.23 μm, D90:8.21 mu m, and 92 parts of activated carbon material in the activated carbon slurry by weight; the adhesive is polytetrafluoroethylene and accounts for 8 parts; the solvent is ethylene carbonate.
The battery is formed by a winding naked electric core of a positive graphite cathode of the NCM523 and the air bag aluminum plastic film packaging bag containing the adsorption layer 2, and the size of the naked electric core is 51 × 90 × 3.5 mm. After the prepared battery core is subjected to hot pressing formation at 45 ℃, secondary sealing operation is not performed, and the thickness of the battery core, the change of the thickness of the battery core before formation and the internal gas production rate of the bagged battery are observed.
Comparative example 2
The gas-pocket-free and selective-permeation-free aluminum-plastic film bagged battery capable of adsorbing gas based on the high-specific-surface-area activated carbon material and provided with the membrane 3 comprises an adsorption layer 2 coated on an aluminum-plastic film; the adsorption layer 2 is 40 μm and is prepared by coating and baking activated carbon slurryAnd (4) carrying out dry rolling to obtain the product. The solid content of the activated carbon slurry is 55 percent, wherein the specific surface area of the activated carbon is 1689m2(iv)/g, particle size distribution D10:1.47 μm, D50:4.23 μm, D90:8.21 mu m, and 92 parts of activated carbon material in the activated carbon slurry by weight; the adhesive is polytetrafluoroethylene and accounts for 8 parts; the solvent is propylene carbonate.
The battery is composed of a winding naked electric core of the NCM523 positive electrode graphite negative electrode and the air bag-free aluminum plastic film packaging bag containing the adsorption layer 2, and the size of the naked electric core is 51 × 90 × 3.5 mm. After the prepared battery core is formed by hot pressing at 45 ℃, the thickness of the battery core, the change of the thickness of the battery core before formation and the internal gas production of the bagged battery are observed.
Comparative example 3
The battery is formed by a winding naked battery cell of a positive graphite cathode of the NCM523 and an aluminum plastic film packaging bag which is provided with an air bag and does not contain an adsorption layer 2, and the size of the naked battery cell is 51 × 90 × 3.5 mm. After the prepared battery core is formed by hot pressing at 45 ℃, the thickness of the battery core, the change of the thickness of the battery core before formation and the internal gas production of the bagged battery are observed.
TABLE 1 gas yield and cell thickness variation after formation
As can be seen from table 1, in terms of gas generation and cell thickness, the data of example 1 is optimal compared with those of comparative examples 2, 3 and 4, and at the same time, compared with the original cell thickness, the cell thickness of example 1 is not significantly increased after formation, which indicates that the pouch battery containing the adsorption layer 2 and the permselectivity film 3 can ignore the existence of gas pockets, and the gas generated in the formation stage can be sufficiently absorbed by the adsorption layer 2.
Example 2
Gas-bag-free aluminum-plastic film bagged battery capable of adsorbing gas based on high-specific-surface-area activated carbon material and gas-bag-free aluminum-plastic film bagged battery capable of adsorbing gasThe battery comprises an adsorption layer 2 coated on an aluminum plastic film and a selective permeation film 3 positioned between the adsorption layer 2 and a naked electric core; the adsorption layer 2 is 70 μm and is prepared by coating, drying and rolling activated carbon slurry. The solid content of the active carbon slurry is 65 percent, wherein the specific surface area of the active carbon is 2100m2(iv)/g, particle size distribution D10: 1.55 μm, D50: 4.84 μm, D90: 9.34 μm, 92 parts of activated carbon material in the activated carbon slurry by weight; the adhesive is vinylidene fluoride and is 5 parts; the solvent is ethyl acetate; the selective permeation membrane 3 is a nylon 6 membrane.
The battery is composed of a winding bare cell of a positive graphite cathode of the NCM523 and the air-bag-free aluminum plastic film packaging bag containing the adsorption layer 2 and the selective permeation film 3, and the size of the bare cell is 51 × 90 × 3.5 mm. The prepared battery is formed at 45 ℃ and then is placed at a high temperature of 85 ℃ under 100% SOC, and the thickness change of the battery core before and after the high-temperature placement, the internal gas production of the bagged battery and the voltage drop K value of the battery are observed.
Comparative example 4
The gas-adsorbable aluminum-plastic film bagged battery with the air bag based on the high-specific-surface-area activated carbon material comprises an adsorption layer 2 coated on an aluminum-plastic film; the adsorption layer 2 is 70 μm and is prepared by coating, drying and rolling activated carbon slurry. The solid content of the active carbon slurry is 65 percent, wherein the specific surface area of the active carbon is 2100m2(iv)/g, particle size distribution D10: 1.55 μm, D50: 4.84 μm, D90: 9.34 mu m, and 92 parts of activated carbon material in the activated carbon slurry by weight; the adhesive is vinylidene fluoride and is 5 parts; the solvent is ethylene carbonate.
The battery is formed by a winding naked electric core of a positive graphite cathode of the NCM523 and the air bag aluminum plastic film packaging bag containing the adsorption layer 2, and the size of the naked electric core is 51 × 90 × 3.5 mm. The prepared battery is formed at 45 ℃, the secondary seal of the air bag is cut off, high-temperature shelving is carried out at 85 ℃ under 100% SOC, and the thickness change of the battery core before and after high-temperature shelving, the internal gas production of the bagged battery and the voltage drop K value of the battery are observed.
Comparative example 5
Adsorbable gas based on high specific surface area activated carbon materialThe aluminum-plastic film bagged battery without the air bag and the selective permeation film 3 comprises an adsorption layer 2 coated on an aluminum-plastic film; the adsorption layer 2 is 70 μm and is prepared by coating, drying and rolling activated carbon slurry. The solid content of the active carbon slurry is 65 percent, wherein the specific surface area of the active carbon is 2100m2(iv)/g, particle size distribution D10: 1.55 μm, D50: 4.84 μm, D90: 9.34 mu m, and 92 parts of activated carbon material in the activated carbon slurry by weight; the adhesive is vinylidene fluoride and is 5 parts; the solvent is propylene carbonate.
The battery is composed of a winding naked electric core of the NCM523 positive electrode graphite negative electrode and the air bag-free aluminum plastic film packaging bag containing the adsorption layer 2, and the size of the naked electric core is 51 × 90 × 3.5 mm. The prepared battery is formed at 45 ℃ and then is placed at a high temperature of 85 ℃ under 100% SOC, and the thickness change of the battery core before and after the high-temperature placement, the internal gas production of the bagged battery and the voltage drop K value of the battery are observed.
Comparative example 6
The battery is composed of a winding naked battery cell of a positive graphite cathode of the NCM523 and an aluminum plastic film packaging bag which is provided with an air bag and does not contain the adsorption layer 2, and the size of the naked battery cell is 51 × 90 × 3.5 mm. And (3) forming the battery at 45 ℃ to cut off the secondary seal of the air bag, then placing the battery at high temperature of 85 ℃ under 100% SOC, and observing the internal gas production of the bagged battery, the thickness change of the battery core before and after placing at high temperature and the voltage drop K value of the battery.
Gas yield and cell thickness variation after standing at high temperature of 85 ℃ under 2100% SOC of table
As can be seen from Table 2, during high-temperature storage, the gas generated from the cell is mainly CO generated by solvolysis at high potential2Gas, as can be seen from the above table, the pouch cell with the activated carbon adsorption layer 2 added thereto has a selectively permeable membrane 3Cell thickness and total gas volume perform best. In comparative examples 4 and 5, which did not include the selective permeation membrane 3, the activated carbon adsorption layer 2 did not completely act on the gas because a part of the electrolyte was adsorbed by the activated carbon adsorption layer 2. While the electrolyte K value results show that example 2 with selectively permeable membrane 3 is the best. The K values of comparative examples 4 and 5 without the permselective membrane 3 were significantly increased because the absence of the permselective membrane 3 caused the electrolyte to be adsorbed by the active material, resulting in deterioration of the electrical properties of the battery, causing an increase in voltage drop. Comparative example 6 resulted in the worst cell thickness and voltage drop due to excessive gas generation.
Example 3
The gas-bag-free aluminum-plastic film bagged battery capable of adsorbing gas based on the high-specific-surface-area activated carbon material comprises an adsorption layer 2 coated on an aluminum-plastic film and a selective permeation film 3 positioned between the adsorption layer and a naked electric core; the adsorption layer 2 is 70 μm and is prepared by coating, drying and rolling activated carbon slurry. The solid content of the active carbon slurry is 63 percent, wherein the specific surface area of the active carbon is 1830m2(iv)/g, particle size distribution D10: 2.82 μm, D50: 6.33 μm, D90: 14.05 mu m, 95 parts of activated carbon material in the activated carbon slurry by weight; the adhesive is polyvinyl alcohol and is 5 parts; the solvent is cyclohexanone and propylene carbonate; the selective permeation membrane 3 is a vinylidene fluoride membrane. After the battery formation, 55 ℃ circulation (1000 circles) experiments are carried out, and the thickness change before and after the battery core circulation and the internal gas production of the bagged battery are observed.
Comparative example 7
The gas-adsorbable aluminum-plastic film bagged battery with the air bag based on the high-specific-surface-area activated carbon material comprises an adsorption layer 2 coated on an aluminum-plastic film; the adsorption layer 2 is 70 μm and is prepared by coating, drying and rolling activated carbon slurry. The solid content of the active carbon slurry is 63 percent, wherein the specific surface area of the active carbon is 1830m2(iv)/g, particle size distribution D10: 2.82 μm, D50: 6.33 μm, D90: 14.05 mu m, 95 parts of activated carbon material in the activated carbon slurry by weight; the adhesive is polyvinyl alcohol and is 5 parts; the solvent is acetonitrile and ethyl acetate.
The battery is formed by a winding naked electric core of a positive graphite cathode of the NCM523 and the air bag aluminum plastic film packaging bag containing the adsorption layer 2, and the size of the naked electric core is 51 × 90 × 3.5 mm. The prepared battery core is hot-pressed at 45 ℃ and then cut off the secondary air bag seal, 55 ℃ circulation (1000 circles) experiment is carried out, and the thickness change before and after the circulation of the battery core and the internal gas production of the bagged battery are observed.
Comparative example 8
The gas-pocket-free and selective-permeation-free aluminum-plastic film bagged battery capable of adsorbing gas based on the high-specific-surface-area activated carbon material and provided with the membrane 3 comprises an adsorption layer 2 coated on an aluminum-plastic film; the adsorption layer 2 is 70 μm and is prepared by coating, drying and rolling activated carbon slurry. The solid content of the active carbon slurry is 63 percent, wherein the specific surface area of the active carbon is 1830m2(iv)/g, particle size distribution D10: 2.82 μm, D50: 6.33 μm, D90: 14.05 mu m, 95 parts of activated carbon material in the activated carbon slurry by weight; the adhesive is polyvinyl alcohol and is 5 parts; the solvent is propylene carbonate.
The battery is composed of a winding naked electric core of the NCM523 positive electrode graphite negative electrode and the air bag-free aluminum plastic film packaging bag containing the adsorption layer 2, and the size of the naked electric core is 51 × 90 × 3.5 mm. After the prepared battery core is subjected to hot pressing formation at 45 ℃, a 55 ℃ circulation (1000 circles) experiment is carried out, and the thickness change before and after the circulation of the battery core and the internal gas production of the bagged battery are observed.
Comparative example 9
The battery is formed by a winding naked battery cell of a positive graphite cathode of the NCM523 and an aluminum plastic film packaging bag without an adsorption layer 2, and the size of the naked battery cell is 51 × 90 × 3.5 mm. After the battery formation, vacuumizing, sealing, cutting off the air bag, circulating at 55 ℃ (1000 circles), and observing the thickness change before and after the battery core circulation and the internal gas production of the bagged battery.
Gas yield and cell thickness variation after 355 ℃ cycle (1000 cycles)
As can be seen from table 3 and fig. 6, the battery of example 3 has the best capacity retention rate, and the capacity fading trend is more linear during the cycle, and no water jump phenomenon occurs, because the adsorption layer 2 adsorbs a large amount of gas, which inhibits the influence of the gas on the electrochemical performance of the battery. In comparative example 7 and comparative example 8, although the adsorption layer 2 is provided, the selective permeation membrane 3 is not provided, and a part of the electrolyte is adsorbed by the adsorption layer 2, so that the electrode wetting is insufficient, the initial performance of the cell is affected, and the initial capacity is low. Comparative example 9 had the worst cycle performance.
The above matters related to the common general knowledge are not described in detail and can be understood by those skilled in the art.
The present invention is not intended to be limited to the particular embodiments shown and described, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (12)
1. A metal composite film capable of adsorbing gas is characterized in that: consists of an aluminum plastic film, an active carbon adsorption layer and a selective permeation film; the active carbon adsorption layer is arranged on the inner side of the aluminum-plastic film, which is in contact with the electrolyte when the aluminum-plastic film is used for packaging the battery; the active carbon adsorption layer is covered with a selective permeation membrane with the area larger than that of the active carbon adsorption layer.
2. The gas-adsorbable metal composite membrane according to claim 1, wherein: the active carbon adsorption layer is formed by coating and drying active carbon slurry; the active carbon slurry comprises an active carbon material, an adhesive and a solvent.
3. The gas-adsorbable metal composite membrane according to claim 2, wherein: the solid content of the activated carbon slurry is 55-65%, wherein the solid content is 92-95 parts by weight of an activated carbon material and 5-8 parts by weight of an adhesive.
4. The gas-adsorbable metal composite membrane according to claim 2, wherein: the activated carbon material has a three-dimensional hierarchical porous structure with micropores, mesopores and macropores; the particle size distribution is 1.40-2.90 μm for D10, 4.20-6.40 μm for D50, and 8.20-14.10 μm for D90.
5. The gas-adsorbable metal composite membrane according to claim 2, wherein: the specific surface area of the activated carbon material is 1600m2/g～2100m2/g。
6. The gas-adsorbable metal composite membrane according to claim 2, wherein: the adhesive is at least one of polytetrafluoroethylene, vinylidene fluoride, styrene butadiene rubber, polyvinyl alcohol, polyethylene and polypropylene.
7. The gas-adsorbable metal composite membrane according to claim 1, wherein: the material of the selective permeation membrane is one selected from polytetrafluoroethylene, vinylidene fluoride and nylon 6.
8. The gas-adsorbable metal composite membrane according to claim 4, wherein: the particle size distribution of the activated carbon material is 1.47-2.82 μm of D10, 4.23-6.33 μm of D50 and 8.21-14.05 μm of D90; the specific surface area of the activated carbon material is 1689m2/g～2100m2/g。
9. The gas-adsorbable metal composite membrane according to claim 5, wherein: the specific surface area of the activated carbon material is 1689m2/g～2100m2/g。
10. The gas-adsorbable metal composite membrane according to claim 1, wherein: the thickness of the activated carbon adsorption layer is 40-70 mu m.
11. A preparation method of a gas-adsorbable metal composite film is characterized by comprising the following steps:
(1) preparing activated carbon slurry:
mixing an activated carbon material, an adhesive and a solvent, and uniformly stirring to obtain the activated carbon slurry; the solid content of the activated carbon slurry is 55-65%, wherein the solid content is 92-95 parts by weight of an activated carbon material and 5-8 parts by weight of an adhesive;
(2) and (3) forming an activated carbon adsorption layer:
uniformly coating the prepared activated carbon slurry on the inner side of the aluminum-plastic film, which is in contact with the electrolyte when the aluminum-plastic film is used for packaging the battery, and drying to form an activated carbon adsorption layer;
(3) preparing the gas-adsorbable metal composite membrane:
and then covering a selective permeation film with the area larger than that of the activated carbon adsorption layer on the activated carbon adsorption layer, wherein the selective permeation film is fixed on the inner side of the aluminum plastic film, which is in contact with the electrolyte when the aluminum plastic film is used for packaging the battery, in a thermoplastic mode.
12. A pouch battery comprising the gas-adsorbable metal composite film according to any one of claims 1 to 10.
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