CN105336884A - Electrochemical cell and preparation method thereof - Google Patents
Electrochemical cell and preparation method thereof Download PDFInfo
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- CN105336884A CN105336884A CN201510715967.2A CN201510715967A CN105336884A CN 105336884 A CN105336884 A CN 105336884A CN 201510715967 A CN201510715967 A CN 201510715967A CN 105336884 A CN105336884 A CN 105336884A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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 of a single cell or a single battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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 of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the field of electrochemical cells, and particularly relates to an electrochemical cell which comprises a cell main body area and a cell packaging area, wherein the cell main body area comprises a positive electrode, a separation film, a negative electrode, an electrolyte and an outer packaging structure; the battery packaging area comprises an effective sealing area, and the battery packaging area comprises a first water-resisting layer, a sealing layer and a second water-resisting layer; the width of the effective sealing area is h, h is more than or equal to 0.5mm and less than or equal to 20mm, the width of an overlapping area of an isolation film contained in the battery main body area and the effective sealing area is d, and h-d is more than or equal to 0.5 mm; that is, the isolation film does not completely penetrate through the effective seal, and the discontinuous isolation film is used in the production of the battery with the structure, so that the size of the overlapping area of the isolation film and the effective seal area can be controlled, the effective seal without the overlapping area of the isolation film, which is wide enough, is obtained, and the packaging reliability is improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical cells, and particularly relates to an electrochemical cell and a preparation method thereof.
Background
After the 21 st century, various electronic device products such as mobile phones, notebooks, wearable devices and the like are in endless, and the lives of the users are greatly enriched; meanwhile, electric vehicles and various energy storage power stations can sprout, develop and grow rapidly like spring bamboo shoots in the rainy season. The above high-tech products have one common feature: high performance, low cost batteries are required to serve as energy storage components.
The existing batteries mainly comprise primary batteries and secondary batteries; the so-called primary battery, which is a battery that cannot be repeatedly charged, mainly includes a carbon zinc battery, an alkaline battery, a paste zinc-manganese battery, a cardboard zinc-manganese battery, an alkaline zinc-manganese battery, a button cell (a button zinc-silver battery, a button lithium-manganese battery, a button zinc-manganese battery), a zinc-air battery, a primary lithium-manganese battery, and the like, and a mercury battery; the secondary battery, i.e., a rechargeable battery, mainly includes a secondary alkaline zinc-manganese battery, a nickel-cadmium rechargeable battery, a nickel-hydrogen rechargeable battery, a lithium rechargeable battery, a lead-acid battery, and a solar battery. Lead-acid batteries can be divided into: open type lead-acid storage battery and totally-enclosed lead-acid storage battery. From the perspective of external packaging, the conventional batteries are mainly classified into flexible-packaged batteries and hard-shell-packaged batteries, and the flexible-packaged battery packaging film has small thickness and large plasticity, so that the battery is widely applied to various high-grade primary batteries and secondary batteries.
However, as the quality of life of people improves, higher requirements, namely longer standby time, are put on electronic products; this requires a higher energy density of the power supply that powers the electronic product.
The existing ways to increase the energy density are: selecting an electrochemical system with higher energy density, such as a high-voltage lithium cobaltate anode, a silicon cathode and the like; a manufacturing process with higher precision is selected, and the consistency of the battery capacity is improved, so that the average capacity of the battery is improved; a substrate having a thinner thickness, such as 6 μm copper foil, 8 μm aluminum foil, 64 μm aluminum plastic film, or the like, is selected. But the high-voltage system has poorer safety performance and higher cost; the silicon cathode has low first efficiency, poor cycle performance and high cost; the high-precision manufacturing process has huge equipment investment and high manufacturing cost; thinner substrates, in turn, tend to mean higher process control requirements, higher material costs; none of these solutions therefore increases the manufacturing costs.
With the increase of personalized electronic products, such as the horizontal emergence of flexible devices, it puts higher requirements on batteries: i.e. a flexible battery. However, in the bending process of the flexible battery, the interface inside the battery core is often a weak link and is easily damaged, so that the performance of the flexible battery is poor; therefore, the number of internal interfaces of the flexible battery is reduced as much as possible, and the method is a reliable method for improving the performance of the flexible battery.
Meanwhile, in order to pursue higher energy density, the width of an effective packaging area is often reduced in the manufacturing process; moreover, new materials and new battery structures are continuously generated, and higher requirements on the packaging reliability of the battery are also provided; and the new battery structure may cause the insulation reliability between the positive electrode and the negative electrode of the battery to be reduced, thereby increasing the self-discharge rate of the battery and causing the battery not to meet the normal use requirement.
In view of the above, there is a need for a new battery and a preparation method thereof, which not only can increase the energy density of the battery, improve the packaging reliability of the battery, reduce the cost (material cost or/and manufacturing cost), improve the self-discharge performance of the battery, but also have excellent flexible performance and electrochemical performance when the battery is a flexible battery.
Disclosure of Invention
The invention aims to: in view of the deficiencies of the prior art, an electrochemical cell is provided, which comprises a cell body region and a cell packaging region, wherein the cell body region comprises a positive electrode, a separation film, a negative electrode, an electrolyte and an outer packaging structure; the battery packaging area comprises an effective sealing area, and the battery packaging area comprises a first water-resisting layer, a sealing layer and a second water-resisting layer; the width of the effective sealing area is h, h is more than or equal to 0.5mm and less than or equal to 20mm, the width of an overlapping area of an isolation film contained in the battery main body area and the effective sealing area is d, and h-d is more than or equal to 0.5 mm; that is, it is indicated that the isolation film does not completely penetrate the effective seal, and when the battery with the structure is produced, a discontinuous isolation film is used (that is, the area of the isolation film corresponding to the single-layer electrode is smaller than the area surrounded by the effective seal area), the size of the overlapping area of the isolation film and the effective seal area can be controlled, so that the wide enough effective seal without the overlapping area of the isolation film is obtained, and the packaging reliability is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
an electrochemical cell comprising a cell body region and a cell packaging region, the cell body region comprising a positive electrode, a separator, a negative electrode, an electrolyte and an outer packaging structure; the battery packaging area comprises an effective packaging area, and the battery packaging area comprises a first water-resisting layer, a sealing layer and a second water-resisting layer; the broadband of the effective sealing area is h, and h is more than or equal to 0.5mm and less than or equal to 20mm, researches show that when the width of the effective sealing area is less than 0.5mm, the effective sealing area cannot play a role of water isolation for a long time (three years or even longer) and can bear the impact force when a battery is subjected to a drop test, and when the length of the effective sealing area is too large, the sealing area occupies the whole volume of the battery, so that the energy density of the battery is reduced; the width of an overlapping area of the isolation film contained in the battery main body area and the effective sealing area is d, and h-d is more than or equal to 0.5mm, namely the isolation film does not completely penetrate through the effective sealing, and the packaging reliability of the effective packaging area can be ensured.
As an improvement of the electrochemical cell of the present invention, 0.8 mm. Ltoreq. H.ltoreq.10mm, 0.8. Ltoreq. H-d.ltoreq.30 mm, and when 20-h-d.ltoreq.30 mm, -10 mm. Ltoreq. D <0, i.e., the width d of the overlapping region of the separation film contained in the cell-body region and the effective seal region is a negative value, it means that the separation film contained in the cell body region and the effective seal region are not but not an overlapping region, and there is a distance of distance d therebetween. At this time, if the first water-resisting layer and the second water-resisting layer are different electrodes, an insulating layer is arranged in a gap between the isolation film contained in the cell body region and the effective sealing region to prevent the two electrodes from being short-circuited; the insulating layer is a sealing layer.
As an improvement of the electrochemical cell of the present invention, the positive electrode comprises a positive coating and a positive current collector, and the negative electrode comprises a negative coating and a negative current collector; the outer packaging structure contains a positive current collector or/and a negative current collector; the battery body region and the battery packaging region are connected together through the positive electrode current collector or/and the negative electrode current collector; the first water barrier layer comprises a positive current collector or/and the second water barrier layer comprises a negative current collector.
As an improvement of the electrochemical cell, a positive current collector contained in the outer packaging structure is coated on one side of a positive electrode, and a positive active substance is contained in a positive single-side coating layer; the negative current collector contained in the outer packaging structure is coated on the single side of the negative electrode, and a negative active substance is contained in a negative single-side coating layer; the positive active material includes at least one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium iron oxide, lithium vanadium oxide, sulfur or sulfide, ternary or multicomponent composite compound, and polyanion cathode material; the negative electrode active material includes at least one of a carbon material, a carbonaceous compound, and a non-carbon material.
As an improvement of the electrochemical cell of the present invention, the electrochemical cell is composed of one single-coated electrode and one single-coated counter electrode, one double-coated electrode and two single-coated counter electrodes (the double-coated electrode is positioned between the two single-coated electrodes), or a plurality of double-coated electrodes and two single-coated electrodes (the double-coated electrode is positioned between the two single-coated electrodes).
As an improvement of the electrochemical cell of the present invention, the separator is an ion conducting, electronically insulating material; the isolating film comprises an isolating film substrate and an adhesive layer, wherein the isolating film substrate is selected from at least one of polypropylene, polyethylene, copolymerized ethylene propylene, polyethylene vinyl acetate copolymer, polyvinylidene fluoride, copolymerized fluoroethylene propylene, polyamide and polyimide and the isolating film after surface treatment; the surface treatment comprises ceramic treatment or/and polymer treatment; the adhesive layer is selected from at least one of polypropylene, polyethylene, modified polypropylene, modified polyethylene and hot melt adhesive.
The invention also comprises a preparation method of the electrochemical cell, which mainly comprises the following steps:
step 1, preparing electrode slurry: uniformly stirring the active substance, the conductive agent, the adhesive and the solvent to obtain electrode slurry for later use;
step 2, preparing an electrode slice: coating the electrode slurry obtained in the step (1) on one surface of a current collector, drying and processing to obtain an electrode plate A with a coating area of length L, width d, area S and a blank foil area around the electrode for later use;
step 3, preparing a finished battery: cutting the isolating membrane into small pieces matched with the electrode slices for later use; and (3) placing the electrode slice obtained in the step (2) on the surface layer, assembling the electrode slice, the isolation film small slice, the sealing layer and the counter electrode to obtain a bare cell, positioning the sealing layer in a hollow foil area around the electrode slice A, and then packaging, forming, shaping and cutting to obtain the electrochemical cell.
As an improvement of the preparation method of the electrochemical cell of the invention, the preparation method of the empty foil area of the electrode with the empty foil area at the periphery in step 2 comprises the steps of intermittently coating (a comb-shaped grid is used for dividing a coating tool bit, wherein the grid width of the grid is d, and the grid width of the grid is m), then carrying out coating operation, coating the slurry obtained in step 1 on a current collector to obtain an initial membrane, optimizing the control precision of equipment and adjusting the coating speed in order to ensure that the coating length and the absolute value of the coating gap are smaller and accurately controlled), cleaning with a solvent (after continuous coating, the coating layer is partially removed by using the solvent to obtain a gap area meeting the specification requirement), cleaning with a laser (after continuous coating, the coating layer is partially removed by using the laser ablation technology to obtain a gap area meeting the specification requirement), stripping the auxiliary layer (namely, an auxiliary layer is preset in the coating gap area, and after continuous coating, the auxiliary layer and a special means are adopted to make the auxiliary layer and the auxiliary layer fall off, thereby achieving the purpose of removing the redundant coating layer to obtain the gap area, for example, a layer is preset in the gap area on the current collector, and then a hot melt adhesive layer is continuously coated, and at least one layer is removed in a hot melting way, so as to obtain the surface of the gap area; and one or more coating layer areas are distributed on the current collector.
As an improvement of the electrochemical cell preparation method of the present invention, the empty foil area of the current collector in step 2 is subjected to an encapsulation auxiliary treatment, wherein the encapsulation auxiliary treatment comprises at least one of polishing treatment, plating treatment (electroplating or chemical plating), organosilicon treatment or anodic oxidation; step 3, in the preparation process of the finished battery, the electrolyte can be sprayed on the pole piece or/and the isolating membrane, or the electrolyte is added into the battery in a liquid injection mode; the isolating film covers the whole coating area and the empty foil area; and (3) both the two surface layers of the battery are the pole pieces prepared in the step (2), and the pole pieces are negative pole pieces or the pole pieces are positive pole pieces or one positive pole piece and one negative pole piece.
As an improvement of the electrochemical cell preparation method of the present invention, in the finished cell preparation process described in step 3, the separator is first cut into small pieces matching with the electrode sheets, the sealing layer is cut into square frames of the required size, the small pieces of separator and the sealing layer square frames are assembled together to form a whole, and then the whole is assembled with the electrode and the counter electrode described in step 2 to obtain the bare cell.
Compared with the prior art, the electrochemical cell and the preparation method thereof have the following advantages:
1. the current collectors of the two single-sided electrodes positioned on the outer side of the battery core are simultaneously used as packaging materials of the battery core, so that the thickness of the battery can be effectively reduced, and the energy density of the battery is improved;
2. when the flexible battery is prepared, the current collector is used as a packaging material, so that the number of interfaces (two interfaces) of the whole battery can be effectively reduced, and the flexibility of the battery and the retention rate of the performance of the battery after bending are increased;
3. the isolation film does not completely penetrate through the effective seal, and a discontinuous isolation film (namely the area of the isolation film corresponding to the single-layer electrode is smaller than the area surrounded by the effective seal area) is used during production of the battery with the structure, so that the size of the overlapping area of the isolation film and the effective seal area can be controlled, and further the wide effective seal without the overlapping area of the isolation film is obtained, the packaging reliability is improved, and the packaging reliability of the sealing layer is influenced due to the existence of the isolation film in the effective seal area;
4. when the method is adopted to prepare the battery cell, in the preparation process, a plurality of single battery cells as a whole flow on a production line, namely, a plurality of battery cells are prepared by one-time production operation (for example, during formation, formation of four battery cells connected together can be completed by one channel), so that the production efficiency is greatly improved, and the production cost is reduced.
Drawings
FIG. 1 is a schematic cross-sectional view of an electrochemical cell of the present invention.
Detailed Description
The present invention and its advantageous effects will be described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Comparative example
Preparing an electrode plate: uniformly stirring lithium cobaltate serving as a positive electrode active substance, PVDF (polyvinylidene fluoride) serving as a binder and a Super-P (N-methyl pyrrolidone) serving as a conductive agent NMP (N-methyl pyrrolidone) serving as a solvent, coating to obtain a single-side coated coil stock which forms a coating area and a hollow foil area along the coating direction and in a direction perpendicular to the coating direction, and then cold-pressing and cutting to obtain a positive plate with the middle coating area and the edge of the hollow foil area; taking graphite as a negative active material, SBR and CMC as adhesives, super-P as a conductive agent and water as a solvent, uniformly stirring, coating to obtain a single-sided coating coil material which forms a coating area and a hollow foil area along the coating direction and perpendicular to the coating direction, and then cold-pressing and cutting to obtain a negative plate with the middle part being a coating area and the edge being the hollow foil area;
preparing a battery: cutting the isolating membrane into a size matched with the size of the electrode, laminating the isolating membrane with the positive plate and the negative plate, arranging a PP layer as an adhesive layer in a hollow foil area around the current collector for packaging, wherein the width h of an effective sealing area is 3mm, the width of an overlapping area of the isolating membrane and the effective sealing area is d, and h-d =0.4mm; and then drying, injecting liquid, forming, shaping, degassing and sealing to obtain a finished battery.
Example 1
As shown in fig. 1, which is a schematic cross-sectional view of a battery corresponding to the present embodiment, the battery is divided into two parts, namely a battery main body 1-1 and a battery packaging region 2-1&2-2, the battery main body region 1-1 is composed of a positive plate, a negative plate and a separation film 5, the positive plate is composed of a positive current collector 3 and a positive coating layer 4, and the negative plate is composed of a negative current collector 1 and a negative coating layer 2; the encapsulation area 2-1 consists of a first water barrier (positive current collector 3), a second water barrier (negative current collector 1 and sealing layer 7; the barrier 5 in the cell body area 1 extends into the sealing layer 7, but does not extend through the entire effective encapsulation area.
The preparation method of the battery comprises the following steps:
preparing an electrode plate: uniformly stirring lithium cobaltate serving as a positive electrode active substance, PVDF (polyvinylidene fluoride) serving as a binder and a Super-P (N-methyl pyrrolidone) serving as a conductive agent NMP (N-methyl pyrrolidone) serving as a solvent, coating to obtain a single-sided coating coil material which forms a coating area and a hollow foil area along the coating direction and in the direction perpendicular to the coating direction, and then cold-pressing to obtain a positive electrode sheet with a coating area at the middle and a hollow foil area at the edge (at the moment, because slitting is not performed, 4 independent coating areas are included on one positive electrode sheet); graphite is used as a negative electrode active substance, SBR and CMC are used as adhesives, super-P is used as a conductive agent, water is used as a solvent, the mixture is uniformly stirred and coated to obtain a single-sided coating coil stock which forms a coating area and a hollow foil area along the coating direction and in the direction vertical to the coating direction, and then the single-sided coating coil stock is cold-pressed to obtain a negative electrode sheet with a coating area at the middle and a hollow foil area at the edge (at the moment, because the negative electrode sheet is not cut, 4 independent coating areas are contained on one positive electrode sheet);
preparing a battery: cutting the isolating membrane into a size matched with the size of the electrode, and then assembling the isolating membrane with the PP used as bonding to obtain four independent isolating membranes which are connected into an integral film by the PP (the PP in the film corresponds to the empty foil area of the electrode slice, and the isolating membrane corresponds to the coating); and drying the positive plate and the negative plate, spraying electrolyte on a film coating area, laminating and packaging the positive plate and the negative plate together with the film, wherein the width H of an effective sealing area (two battery cores) is 6mm, so as to obtain a whole formed by connecting four battery cores together, then forming, degassing and sealing the whole, and finally cutting the whole along the central line of the effective sealing area, so as to obtain a finished product battery core (the width H of the single-battery-core effective sealing area is 3mm, the width d of an overlapping area of an isolation film and the effective sealing area, and H-d =1.2 mm).
The rest is the same as the comparative example and is not described again;
example 2
The method is different from the embodiment 1 in that the method comprises the following steps:
preparing a battery: cutting the isolating membrane into a size matched with the size of the electrode, and then assembling the isolating membrane with the PP used as bonding to obtain four independent isolating membranes which are connected into an integral film by the PP (the PP in the film corresponds to the empty foil area of the electrode slice, and the isolating membrane corresponds to the coating); and drying the positive plate and the negative plate, spraying electrolyte on a film coating area, laminating and packaging the positive plate and the negative plate together with the film, wherein the width H of an effective sealing area (two battery cores) is 6mm, so as to obtain a whole formed by connecting four battery cores together, then forming, degassing and sealing the whole, and finally cutting the whole along the central line of the effective sealing area, so as to obtain a finished product battery core (the width H of the single-battery-core effective sealing area is 3mm, the width d of an overlapping area of an isolation film and the effective sealing area, and H-d =0.5 mm).
The rest is the same as the embodiment 1, and the description is omitted.
Example 3
The difference from the embodiment 1 is that the method comprises the following steps:
preparing a battery: cutting the isolating membrane into a size matched with the size of the electrode, and then assembling the isolating membrane with PP serving as bonding to obtain four independent isolating membranes, wherein the four independent isolating membranes are connected into an integral thin membrane by the PP (the PP in the thin membrane corresponds to a hollow foil area of the electrode plate, and the isolating membrane corresponds to the coating); and drying the positive plate and the negative plate, spraying electrolyte on a film coating area, laminating and packaging the positive plate and the negative plate together with the film, wherein the width H of an effective sealing area (two battery cores) is 6mm, so as to obtain a whole formed by connecting four battery cores together, then forming, degassing and sealing the whole, and finally cutting the whole along the central line of the effective sealing area, so as to obtain a finished product battery core (the width H of the single-battery-core effective sealing area is 3mm, the width d of an overlapping area of an isolation film and the effective sealing area, and H-d =0.8 mm).
The rest is the same as embodiment 1, and the description is omitted.
Example 4
The method is different from the embodiment 1 in that the method comprises the following steps:
preparing an electrode plate: uniformly stirring lithium cobaltate serving as a positive electrode active substance, PVDF (polyvinylidene fluoride) serving as a binder and a Super-P (N-methyl pyrrolidone) serving as a conductive agent NMP (N-methyl pyrrolidone) serving as a solvent, coating to obtain a single-sided coating coil material which forms a coating area and a hollow foil area along the coating direction and in the direction perpendicular to the coating direction, and then cold-pressing to obtain a positive electrode sheet with a coating area at the middle and a hollow foil area at the edge (at the moment, because slitting is not performed, 4 independent coating areas are included on one positive electrode sheet); graphite is used as a negative electrode active substance, SBR and CMC are used as adhesives, super-P is used as a conductive agent, water is used as a solvent, the mixture is uniformly stirred and coated to obtain a single-sided coating coil stock which forms a coating area and a hollow foil area along the coating direction and in the direction vertical to the coating direction, and then the single-sided coating coil stock is cold-pressed to obtain a negative electrode sheet with a coating area at the middle and a hollow foil area at the edge (at the moment, because the negative electrode sheet is not cut, 4 independent coating areas are contained on one positive electrode sheet);
preparing a battery: cutting the isolating membrane into a size matched with the size of the electrode, and then assembling the isolating membrane with PP serving as bonding to obtain four independent isolating membranes, wherein the four independent isolating membranes are connected into an integral thin membrane by the PP (the PP in the thin membrane corresponds to a hollow foil area of the electrode plate, and the isolating membrane corresponds to the coating); drying the positive plate and the negative plate, spraying electrolyte on a film coating area, laminating and packaging the positive plate and the negative plate together with the film, wherein the width H of an effective sealing area (two electric cores) is 40mm, obtaining a whole body formed by connecting four electric cores together, forming, degassing and sealing the film, and finally cutting the film along the central line of the effective sealing area to obtain a finished product electric core (the width of a single-electric-core effective sealing area H is 20mm, the width of an overlapping area of an isolation film and the effective sealing area is d, H-d =30mm, the distance between the isolation film and a sealing edge is 10mm, the isolation film and the sealing edge do not have the overlapping area, and wider PP is used for blocking electronic conduction between the positive plate and the negative plate).
The rest is the same as embodiment 1, and the description is omitted.
Example 5
The method is different from the embodiment 4 in that the method comprises the following steps:
preparing an electrode plate: uniformly stirring and coating lithium cobaltate serving as a positive electrode active substance, PVDF serving as a bonding agent and Super-P serving as a conductive agent NMP serving as a solvent to obtain single-side coated coil materials which form a coating area and an empty foil area along the coating direction and in a direction vertical to the coating direction, and then cold-pressing to obtain a positive plate of which the middle is a coating area and the edge of the empty foil area (at the moment, because slitting is not performed, 4 independent coating areas are included on one positive plate); graphite is used as a negative electrode active substance, SBR and CMC are used as adhesives, super-P is used as a conductive agent, water is used as a solvent, the mixture is uniformly stirred and coated to obtain a single-side coating coil stock which forms a coating area and an empty foil area along the coating direction and the direction vertical to the coating direction, and then the single-side coating coil stock is cold-pressed to obtain a negative electrode sheet of which the middle is a coating area and the edge is an empty foil area (at the moment, because slitting is not carried out, 4 independent coating areas are contained in one positive electrode sheet);
preparing a battery: cutting the isolating membrane into a size matched with the size of the electrode, and then assembling the isolating membrane with the PP used as bonding to obtain four independent isolating membranes which are connected into an integral film by the PP (the PP in the film corresponds to the empty foil area of the electrode slice, and the isolating membrane corresponds to the coating); drying the positive plate and the negative plate, spraying electrolyte on a film coating area, laminating and packaging the positive plate and the negative plate together with the film, wherein the width H of an effective sealing area (two battery cells) is 20mm, obtaining a whole with four battery cells connected together, and then forming, degassing and sealing the whole, and finally cutting the whole along the central line of the effective sealing area to obtain a finished product battery cell (the width of the single battery cell effective sealing area H is 10mm, the width of an overlapping area of a separation film and the effective sealing area is d, H-d =11mm, the distance of the separation film from a sealing edge is 1mm, the separation film and the sealing edge do not have the overlapping area, and wider PP (polypropylene) is used for blocking electronic conduction between the positive plate and the negative plate).
The rest is the same as the embodiment 1, and the description is omitted.
Example 6
The method is different from the embodiment 1 in that the method comprises the following steps:
preparing a multi-electrode sheet: uniformly stirring and coating lithium cobaltate serving as a positive electrode active substance, PVDF serving as a bonding agent and Super-P serving as a conductive agent NMP serving as a solvent to obtain single-side coated coil materials which form a coating area and an empty foil area along the coating direction and in a direction vertical to the coating direction, and then cold-pressing to obtain a positive plate of which the middle is a coating area and the edge of the empty foil area (at the moment, because slitting is not performed, 4 independent coating areas are included on one positive plate); graphite is used as a negative electrode active substance, SBR and CMC are used as adhesives, super-P is used as a conductive agent, water is used as a solvent, the mixture is uniformly stirred and coated to obtain a single-side coating coil stock which forms a coating area and an empty foil area along the coating direction and the direction vertical to the coating direction, and then the single-side coating coil stock is cold-pressed to obtain a negative electrode sheet of which the middle is a coating area and the edge is an empty foil area (at the moment, because slitting is not carried out, 4 independent coating areas are contained in one positive electrode sheet);
preparing a battery: cutting the isolating membrane into a size matched with the size of the electrode, and then assembling the isolating membrane with PP serving as bonding to obtain four independent isolating membranes, wherein the four independent isolating membranes are connected into an integral thin membrane by the PP (the PP in the thin membrane corresponds to a hollow foil area of the electrode plate, and the isolating membrane corresponds to the coating); drying the positive plate and the negative plate, spraying electrolyte on a film coating area, laminating and packaging the positive plate and the negative plate together with the film, wherein the width H of an effective sealing area (two electric cores) is 10mm, obtaining a whole body formed by connecting four electric cores together, forming, degassing and sealing the film, and finally cutting the film along the central line of the effective sealing area to obtain a finished product electric core (the width of a single electric core effective sealing area H is 5mm, the width of an overlapping area of an isolation film and the effective sealing area is d, H-d =5mm, the distance between the isolation film and a sealing edge is 0mm at the moment, the isolation film and the sealing edge are connected, and the PP which is just wider needs to be used at the moment for blocking electronic conduction between the positive plate and the negative plate).
The rest is the same as the embodiment 1, and the description is omitted.
Example 7
The method is different from the embodiment 1 in that the method comprises the following steps:
preparing a multi-electrode sheet: uniformly stirring lithium cobaltate serving as a positive electrode active substance, PVDF (polyvinylidene fluoride) serving as a binder and a Super-P (N-methyl pyrrolidone) serving as a conductive agent NMP (N-methyl pyrrolidone) serving as a solvent, coating to obtain a single-sided coating coil material which forms a coating area and a hollow foil area along the coating direction and in the direction perpendicular to the coating direction, and then cold-pressing to obtain a positive electrode sheet with a coating area at the middle and a hollow foil area at the edge (at the moment, because slitting is not performed, 4 independent coating areas are included on one positive electrode sheet); graphite is used as a negative electrode active substance, SBR and CMC are used as adhesives, super-P is used as a conductive agent, water is used as a solvent, the mixture is uniformly stirred and coated to obtain a single-sided coating coil stock which forms a coating area and a hollow foil area along the coating direction and in the direction vertical to the coating direction, and then the single-sided coating coil stock is cold-pressed to obtain a negative electrode sheet with a coating area at the middle and a hollow foil area at the edge (at the moment, because the negative electrode sheet is not cut, 4 independent coating areas are contained on one positive electrode sheet);
preparing a battery: cutting the ceramic processing isolation membrane (the surface of the isolation membrane is coated with a layer of ceramic with the thickness of 2 mu m) into the size matched with the size of the electrode, and then assembling the ceramic processing isolation membrane and the PP used as bonding to obtain four independent ceramic processing isolation membranes which are connected into an integral thin film by the PP (the PP in the thin film corresponds to the empty foil area of the electrode slice, and the ceramic processing isolation membrane corresponds to the coating); and drying the positive plate and the negative plate, spraying electrolyte on a film coating area, laminating and packaging the positive plate and the negative plate together with the film, wherein the width H of an effective sealing area (two battery cores) is 8mm, so as to obtain a whole formed by connecting four battery cores together, then forming, degassing and sealing the whole, and finally cutting the whole along the central line of the effective sealing area, so as to obtain a finished product battery core (the width of a single-battery-core effective sealing area H is 4mm, the width of an overlapping area of an isolation film and the effective sealing area is d, and H-d =3 mm).
The rest is the same as embodiment 1, and the description is omitted.
Example 8
The difference from the embodiment 7 is that the method comprises the following steps:
preparing a multi-electrode sheet: uniformly stirring and coating lithium cobaltate serving as a positive electrode active substance, PVDF serving as a bonding agent and Super-P serving as a conductive agent NMP serving as a solvent to obtain single-side coated coil materials which form a coating area and an empty foil area along the coating direction and in a direction vertical to the coating direction, and then cold-pressing to obtain a positive plate of which the middle is a coating area and the edge of the empty foil area (at the moment, because slitting is not performed, 4 independent coating areas are included on one positive plate); graphite is used as a negative electrode active substance, SBR and CMC are used as adhesives, super-P is used as a conductive agent, water is used as a solvent, the mixture is uniformly stirred and coated to obtain a single-sided coating coil stock which forms a coating area and a hollow foil area along the coating direction and in the direction vertical to the coating direction, and then the single-sided coating coil stock is cold-pressed to obtain a negative electrode sheet with a coating area at the middle and a hollow foil area at the edge (at the moment, because the negative electrode sheet is not cut, 4 independent coating areas are contained on one positive electrode sheet);
preparing a battery: cutting the ceramic processing isolation membrane into a size matched with the size of the electrode, and then assembling the ceramic processing isolation membrane and PP serving as bonding to obtain four independent ceramic processing isolation membranes, wherein the four independent ceramic processing isolation membranes are connected into an integral thin membrane by the PP (the PP in the thin membrane corresponds to a hollow foil area of the electrode plate, and the ceramic processing isolation membrane corresponds to the coating); drying the positive plate and the negative plate, spraying electrolyte on a film coating area, laminating and packaging the positive plate and the negative plate together with the film, wherein the width H of an effective sealing area (two battery cores) is 1mm, obtaining a whole body formed by connecting four battery cores together, forming, degassing and sealing the whole body, and finally cutting the whole body along the central line of the effective sealing area to obtain a finished product battery core (the width H of a single battery core effective sealing area is 0.5mm, the width of an overlapping area of a ceramic treatment isolating film and the effective sealing area is d, H-d =1.5mm, the distance from the sealing edge of the ceramic treatment isolating film is-1 mm at the moment, no overlapping area exists between the ceramic treatment isolating film and the sealing edge, and at the moment, wider PP is required to be used for blocking electronic conduction between the positive plate and the negative plate).
The rest is the same as example 7 and will not be described again.
Example 9
The difference from the embodiment 1 is that the method comprises the following steps:
preparing a multi-electrode sheet: uniformly stirring lithium cobaltate serving as a positive electrode active substance, PVDF (polyvinylidene fluoride) serving as a binder and a Super-P (N-methyl pyrrolidone) serving as a conductive agent NMP (N-methyl pyrrolidone) serving as a solvent, coating to obtain a single-sided coating coil material which forms a coating area and a hollow foil area along the coating direction and in the direction perpendicular to the coating direction, and then cold-pressing to obtain a positive electrode sheet with a coating area at the middle and a hollow foil area at the edge (at the moment, because slitting is not performed, 4 independent coating areas are included on one positive electrode sheet); graphite is used as a negative electrode active substance, SBR and CMC are used as adhesives, super-P is used as a conductive agent, water is used as a solvent, the mixture is uniformly stirred and coated to obtain a single-side coating coil stock which forms a coating area and an empty foil area along the coating direction and the direction vertical to the coating direction, and then the single-side coating coil stock is cold-pressed to obtain a negative electrode sheet of which the middle is a coating area and the edge is an empty foil area (at the moment, because slitting is not carried out, 4 independent coating areas are contained in one positive electrode sheet);
preparing a battery: cutting the ceramic processing isolation membrane into a size matched with the size of the electrode, and then assembling the ceramic processing isolation membrane and PP serving as bonding to obtain four independent ceramic processing isolation membranes, wherein the four independent ceramic processing isolation membranes are connected into an integral thin membrane by the PP (the PP in the thin membrane corresponds to a hollow foil area of the electrode plate, and the ceramic processing isolation membrane corresponds to the coating); drying the positive plate and the negative plate, spraying electrolyte on a film coating area, laminating and packaging the positive plate and the negative plate together with the film, wherein the width H of an effective sealing area (two battery cells) is 1.6mm, obtaining a whole body formed by connecting four battery cells together, forming, degassing and sealing the whole body, and finally cutting the whole body along the central line of the effective sealing area to obtain a finished battery cell (the width H of the single battery cell effective sealing area is 0.8mm, the width of an overlapping area of a ceramic treatment isolating film and the effective sealing area is d, H-d =1.8mm, the distance of the ceramic treatment isolating film from a sealing edge is-1 mm, the two areas do not have an overlapping area, and at the moment, wider PP (polypropylene) is required to be used for blocking electronic conduction between the positive plate and the negative plate). The rest is the same as the embodiment 1, and the description is omitted.
And (3) capacity testing: the capacity of the battery cells of the comparative examples and the embodiment is tested in an environment at 35 ℃ according to the following flow: standing for 3min; charging to 4.2V at constant current of 0.5C and charging to 0.05C at constant voltage; standing for 3min; discharging at constant current of 0.5C to 3.0V to obtain first discharge capacity D0; standing for 3min to complete the capacity test; the results are shown in Table 1.
Self-discharge test: from each of comparative examples and examples 1 to 9, 30 cells were taken out and subjected to a self-discharge test: charging to 3.8V by using 0.5C in an environment at 35 ℃, and enabling CV to be 0.05C; and then taking out the battery core, standing for 48 hours in an environment at 45 ℃, wherein the test voltage is V1, standing for 72 hours at room temperature, and then the test voltage is V2, wherein the self-discharge rate of the battery is = (V1-V2)/72 (mV/h), and the average value is counted in the table 1.
Testing the packaging reliability: from each of comparative examples and examples 1 to 9, 10 cells were taken out and subjected to a mounting reliability test: charging to 3.8V with 0.5C in 35 ℃ environment, and CV to 0.05C; then taking out the cell to test the thickness of the cell to be h1, then placing the cell in an environment with 70 ℃ and 95% humidity for 7 days, and taking out the cell to test the thickness of the cell to be h2; calculating the thickness expansion rate: (h 2-h 1)/h 1 x 100%; when (h 2-h 1)/h 1 > 100% >10%, package failure is noted and the results are tabulated in table 1.
TABLE 1 electric Properties of the batteries of comparative example and example
Comparing the comparative examples with various embodiments, when the method of the present invention is used to prepare the battery cell of the present invention, several single battery cells as a whole flow on a production line in the preparation process, that is, a plurality of battery cells are prepared by one production operation (for example, when formation is performed, formation of four battery cells connected together can be completed by one channel), thereby greatly improving the production efficiency and reducing the production cost.
As can be seen from table 1, the battery cell of the present invention has high capacity performance, low self-discharge rate, and high package reliability.
Specifically, as can be seen from examples 1 to 3, when h-d is small, the package reliability is affected because the isolation film in the sealing layer affects the packaging effect of the seal, and therefore the value of the effective packaging region excluding the width of the overlapping region of the isolation film and the effective sealing region cannot be too low.
From the embodiments 4 to 7, when the width of the overlapping region between the isolation film and the effective sealing region is too small, even when there is no overlapping region, the self-discharge rate of the battery is high, because the PP and the isolation film cannot be organically connected into a complete whole to block the electron transmission between the positive electrode and the negative electrode; furthermore, when the width of the overlapping region between the separator and the effective sealing region is negative, it is often necessary to use an adhesive material to compensate for the shortage of the separator, and since the adhesive material does not have ion transport properties, the battery capacity performance is affected, and the battery capacity is reduced.
From examples 7 to 9, the self-discharge rate of the battery prepared from the ceramic separator was significantly lower; when the effective sealing width h is too small, the packaging reliability of the battery is affected.
Variations and modifications to the above-described embodiments may become apparent to those skilled in the art to which the invention pertains based upon the disclosure and teachings of the above specification. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious modifications, substitutions or alterations based on the present invention will fall within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. An electrochemical cell comprising a cell body region and a cell package region, the cell body region comprising a positive electrode, a separator, a negative electrode, an electrolyte and an outer package structure; the battery packaging area comprises an effective packaging area, and the battery packaging area comprises a first water-resisting layer, a sealing layer and a second water-resisting layer; the method is characterized in that: the width of the effective sealing area is h, h is more than or equal to 0.5mm and less than or equal to 20mm, the width of an overlapping area of the isolation film contained in the battery main body area and the effective sealing area is d, and h-d is more than or equal to 0.5 mm.
2. An electrochemical cell according to claim 1, wherein 0.8mm ≤ h ≤ 10mm,0.8 ≤ h-d ≤ 30mm, and when 20 h-d ≤ 30mm, -10mm ≤ d <0, an insulating layer is provided in a gap between the separation film included in the cell-body region and the effective sealing region if the first water-barrier layer and the second water-barrier layer are different electrodes; the insulating layer is a sealing layer.
3. The electrochemical cell of claim 1, wherein the positive electrode comprises a positive coating and a positive current collector, and the negative electrode comprises a negative coating and a negative current collector; the outer packaging structure contains a positive current collector or/and a negative current collector; the battery body region and the battery packaging region are connected together through the positive electrode current collector or/and the negative electrode current collector; the first water-resisting layer comprises a positive electrode current collector or/and the second water-resisting layer comprises a negative electrode current collector.
4. The electrochemical cell as claimed in claim 3, wherein the positive electrode current collector included in the outer packaging structure is coated on one side of the positive electrode, and the coating layer on one side of the positive electrode contains a positive electrode active material; the negative current collector contained in the outer packaging structure is coated on the single side of the negative electrode, and a negative active substance is contained in a negative single-side coating layer; the positive active material includes at least one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium iron oxide, lithium vanadium oxide, sulfur or sulfide, ternary or multicomponent composite compound, and polyanion cathode material; the negative electrode active material includes at least one of a carbon material, a carbonaceous compound, and a non-carbon material.
5. An electrochemical cell according to claim 1, wherein the electrochemical cell comprises a single coated electrode and a single coated counter electrode, a double coated electrode and two single coated counter electrodes, or a plurality of double coated electrodes and two single coated electrodes.
6. An electrochemical cell according to claim 2, wherein the separator is an ionically conducting electronically insulating material; the isolating film comprises an isolating film substrate and an adhesive layer, wherein the isolating film substrate is selected from at least one of polypropylene, polyethylene, copolymerized ethylene propylene, polyethylene vinyl acetate copolymer, polyvinylidene fluoride, copolymerized fluoroethylene propylene, polyamide and polyimide and a surface-treated isolating film; the surface treatment comprises ceramic treatment or/and polymer treatment; the adhesive layer is selected from at least one of polypropylene, polyethylene, modified polypropylene, modified polyethylene and hot melt adhesive.
7. A method of making an electrochemical cell according to claim 1, comprising the steps of:
step 1, preparing electrode slurry: uniformly stirring the active substance, the conductive agent, the adhesive and the solvent to obtain electrode slurry for later use;
step 2, preparing an electrode slice: coating the electrode slurry obtained in the step (1) on one surface of a current collector, drying and processing to obtain an electrode slice A with a coating area of length L, width d, area S and a hollow foil area around the electrode for later use;
step 3, preparing a finished battery: cutting the isolating membrane into small pieces matched with the electrode slices for later use; and (3) placing the electrode slice obtained in the step (2) on the surface layer, assembling the electrode slice, the small isolation membrane, the sealing layer and the counter electrode to obtain a bare cell, positioning the sealing layer in a hollow foil area around the electrode slice A, and then packaging, forming, shaping and cutting to obtain the electrochemical cell.
8. A method of making an electrochemical cell according to claim 8, wherein: step 2, the preparation method of the empty foil area of the electrode with the empty foil area at the periphery comprises at least one of intermittent coating, solvent cleaning, laser cleaning and auxiliary layer stripping; and one or more coating layer regions are distributed on the current collector.
9. A method for preparing the electrochemical cell according to claim 8, wherein the empty foil region of the current collector in step 2 is subjected to an encapsulation auxiliary treatment, the encapsulation auxiliary treatment comprises at least one of polishing, plating, silicone treatment or anodic oxidation; 3, in the preparation process of the finished battery, spraying the electrolyte on the pole piece or/and the isolating membrane, or adding the electrolyte into the battery by adopting an electrolyte injection mode; the isolating film covers the whole coating area and the empty foil area; and (3) the two surface layers of the battery are both the pole pieces prepared in the step (2), and the pole pieces are both negative pole pieces or the pole pieces are both positive pole pieces or one positive pole piece and one negative pole piece.
10. A method for preparing an electrochemical cell according to claim 8, wherein in the step 3, during the preparation of the finished cell, the separator is first cut into small pieces matching with the electrode sheets, the sealing layer is cut into square frames with required size, then the small pieces of separator and the square frames of sealing layer are assembled together to form a whole, and then the whole is assembled with the electrode and the counter electrode in the step 2 to obtain a bare cell.
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| CN107302104A (en) * | 2016-04-15 | 2017-10-27 | 宁德新能源科技有限公司 | Improve method of flexible packing lithium ion battery energy density and products thereof |
| CN108023117A (en) * | 2017-11-30 | 2018-05-11 | 北京国能电池科技有限公司 | Lithium ion battery of high-energy-density and preparation method thereof |
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| CN204614884U (en) * | 2015-06-03 | 2015-09-02 | 惠州市恒泰科技有限公司 | A kind of power-type power, energy storage lithium ion battery and Li-ion batteries piles |
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