CN116722150A - Composite foil and application thereof - Google Patents
Composite foil and application thereof Download PDFInfo
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- CN116722150A CN116722150A CN202310805427.8A CN202310805427A CN116722150A CN 116722150 A CN116722150 A CN 116722150A CN 202310805427 A CN202310805427 A CN 202310805427A CN 116722150 A CN116722150 A CN 116722150A
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- layer
- composite foil
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- conductive layer
- hole
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- 239000011888 foil Substances 0.000 title claims abstract description 113
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 239000011148 porous material Substances 0.000 claims abstract description 91
- 239000000758 substrate Substances 0.000 claims abstract description 77
- 239000007822 coupling agent Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 230000003750 conditioning effect Effects 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 239000012756 surface treatment agent Substances 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 239000012528 membrane Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 12
- 230000000149 penetrating effect Effects 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 150000001913 cyanates Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- -1 polypropylene Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Chemical class 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229920001971 elastomer Chemical class 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Chemical class 0.000 description 1
- 239000005020 polyethylene terephthalate Chemical class 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001155 polypropylene Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
Abstract
The invention provides a composite foil and application thereof, wherein the composite foil comprises a substrate layer and a conductive layer on at least one side surface of the substrate layer, the composite foil is provided with a hole structure, the ratio of the aperture of a hole to the depth of the hole is 1/200-110, wherein D is the aperture, and H is the depth of the hole; the composite foil material has the advantages that the weight of the foil material is reduced, the energy density is improved, the elongation rate and the stripping force of the foil material are also improved, the elongation rate is improved, the stress concentration is avoided, and the safety performance of a battery is improved by arranging the special specific depth ratio hole structure; meanwhile, the risk that lithium dendrites pierce through the membrane is reduced due to the arrangement of the pore structure, so that the safety performance of the battery is further improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a composite foil and application thereof.
Background
Lithium ion batteries have been widely used as energy storage devices for various mobile devices, and the demands of the market for energy density and safety of lithium ion batteries are increasing. At present, commercial lithium ion battery composite foil materials mainly comprise pure copper foil and pure aluminum foil, but the copper foil and the aluminum foil have large density and high weight, and the energy density of the copper foil and the aluminum foil for lithium ion batteries is limited.
In order to reduce the weight of the composite foil, the prior art developed a composite foil to replace the metal foil as the composite foil of the lithium ion battery. Compared with the metal foil, the composite foil has lighter weight, lower cost and better safety performance; however, the elongation percentage of the composite foil in the prior art is insufficient, so that the composite foil is easy to break during the battery charging and discharging or winding process, and the safety of the prepared battery is reduced. In addition, the composite foil in the prior art has low stripping force due to the existence of the heterogeneous interface, and dendrites are easy to generate when active substances are coated on the surface of the existing composite foil, so that the risk that the dendrites pierce through the battery membrane exists, and the safety of the battery is reduced.
Based on the above studies, it is required to provide a composite foil capable of improving energy density, safety performance, peeling force, and ductility while ensuring electrode performance.
Disclosure of Invention
The invention aims to provide a composite foil and application thereof, wherein in the composite foil, the arrangement of a specific diameter-depth ratio hole structure does not influence the normal performance of an electrode, reduces the weight of the foil, improves the energy density, improves the elongation and stripping force of the foil, improves the elongation, avoids stress concentration, and meanwhile, the arrangement of the hole structure reduces the risk of penetrating a diaphragm by lithium dendrites, so that the safety performance is improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a composite foil, which comprises a substrate layer and a conductive layer on at least one side surface of the substrate layer, wherein the composite foil is provided with a pore structure, the ratio of the pore diameter to the pore depth of the pores is 1/200-110, wherein D is the pore diameter, and H is the pore depth.
The aperture refers to the maximum width of the hole.
The composite foil material reduces the weight of the composite foil material by arranging the hole structure, improves the energy density of the battery, improves the elongation and the peeling force of the composite foil material by controlling the D/H value of the hole diameter-depth ratio, solves the problem of lower elongation and peeling force of the traditional composite foil material, and further reduces the peeling force and the elongation due to the fact that the stress of the composite foil material is concentrated if the D/H value is too large, and cannot improve the peeling force and the elongation of the composite foil material if the D/H value is too small.
The ratio of pore diameter to pore depth of the pores is 1/200.ltoreq.D/H.ltoreq.110, and may be, for example, 1/200, 1/150, 1/100, 1/50, 1/10, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or 110, but not limited to the values recited, other non-recited values within the numerical range are equally applicable, preferably 1/200.ltoreq.D/H.ltoreq.100.
Preferably, D is 0.1-10 μm, for example, 0.1 μm, 1 μm, 3 μm, 5 μm, 7 μm or 10 μm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, H is 0.1-20 μm, for example, 0.1 μm, 1 μm, 5 μm, 10 μm, 15 μm or 20 μm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the ratio of the pore diameter to the pore depth of the pores in the substrate layer is 1/80.ltoreq.D 1 /H 1 Less than or equal to 50, wherein D 1 For the aperture of the holes in the substrate layer, H 1 The depth of the holes in the basal layer is equal to or less than 1/80 of D 1 /H 1 And 50. Ltoreq.50, may be, for example, 1/80, 1/65, 1/50, 1/25, 1/10, 1, 10, 20, 30, 40 or 50, but are not limited to the values recited, other values not recited in the numerical range being equally applicable.
Preferably, in the conductive layer, the ratio of the pore diameter to the pore depth of the pores is 1/200.ltoreq.D 2 /H 2 Less than or equal to 80, wherein D 2 Is the pore diameter of the pores in the conductive layer, H 2 The hole depth of the holes in the conductive layer is equal to or less than 1/200 of D 2 /H 2 80, for example 1/200, 1/150, 1/100, 1/50, 1, 10, 20, 30, 40, 50, 60, 70 or 80, but are not limited to the values recited, other non-recited values within the range of values are equally applicable, preferably 1/180D 2 /H 2 ≤80。
The composite foil comprises a substrate layer and a conductive layer, wherein the substrate layer and the conductive layer are different in material, different in function and different in position relation with the electrode active coating, so that the hole depth ratio of the substrate layer and the conductive layer is different, and when the hole diameter depth ratio in the substrate layer is 1/80-D 1 /H 1 In the range of less than or equal to 50 percent, the diameter-depth ratio of the holes in the conductive layer is less than or equal to 1/180 and less than or equal to D 2 /H 2 When the elongation and the stripping force of the composite foil are less than or equal to 80, the elongation and the stripping force of the composite foil can be further improved.
Preferably, said D 1 0.1 to 5. Mu.m, for example 0.1. Mu.m, 1. Mu.m, 2. Mu.m, 3. Mu.m, 4. Mu.m, or 5. Mu.m, H 1 For example, the range of 0.1 to 8. Mu.m, may be 0.1. Mu.m, 1. Mu.m, 2. Mu.m, 3. Mu.m, 4. Mu.m, 5. Mu.m, 6. Mu.m, 7. Mu.m, or 8. Mu.m, but not limited to the values recited, and other values not recited in the numerical range are applicable.
Preferably, said D 2 0.1 to 10. Mu.m, for example 0.1. Mu.m, 1. Mu.m, 2. Mu.m, 3. Mu.m, 4. Mu.m, 5. Mu.m, 6. Mu.m, 7. Mu.m, 8. Mu.m, 9. Mu.m, or 10. Mu.m, H 2 For example, the range of 0.1 to 18. Mu.m, may be 0.1. Mu.m, 1. Mu.m, 3. Mu.m, 5. Mu.m, 7. Mu.m, 9. Mu.m, 11. Mu.m, 13. Mu.m, 15. Mu.m, 17. Mu.m, or 18. Mu.m, but not limited to the values recited, and other values not recited in the numerical range are applicable.
Preferably, the holes in the base layer and the conductive layer are staggered.
Preferably, the holes in the base layer and the conductive layer are independently through holes and/or blind holes, respectively.
The hole structure of the composite foil can be a through hole penetrating through the conductive layer and the substrate layer, namely, the hole of the conductive layer is communicated with the hole of the substrate layer; the conductive layer and/or the substrate layer may be through holes, but the hole structures of the substrate layer and the conductive layer are staggered; the blind holes which do not completely penetrate through the substrate layer and/or the conductive layer respectively can be formed, but the hole structures of the substrate layer and the conductive layer are arranged in a staggered manner; the through holes penetrating through the conductive layer or blind holes not penetrating through the substrate layer can also be used, but the hole structures of the substrate layer and the conductive layer are mutually staggered; or through holes penetrating through the substrate layer or blind holes not penetrating through the substrate layer, but the hole structures of the substrate layer and the conductive layer are staggered with each other.
According to the invention, the holes of the conductive layer and the holes of the substrate layer are arranged in a staggered manner, and the staggered arrangement can further disperse the stress of the composite foil so that the heterogeneous materials can be better adapted to each other, stress concentration is avoided, the composite foil still has stronger pulling capability in the heterogeneous interface, and the stripping force, the extensibility and the safety performance of the composite foil are improved. The blind holes which are arranged in a staggered way on the substrate layer and the conductive layer can be arranged on one surface of the conductive layer and the substrate layer, and the same surface or surfaces far away from each other; may be provided on both surfaces of the conductive layer and the base layer at the same time.
The shape of the hole may be square, circular, oval or irregular, and circular holes are preferable in order to reduce stress concentration. In addition, the pore diameter of the through-hole or blind hole extending from the hole surface to the hole bottom may be consistent with the surface pore diameter, or the pore diameter extending from the hole surface to the hole bottom may be gradually decreased or gradually increased. Of these, it is preferable that the pore diameter extending from the pore surface to the pore bottom can be kept uniform with the surface pore diameter.
Preferably, the composite foil has an average pore density of 1-10000 pores/mm 2 For example, 1/mm 2 2000 pieces/mm 2 4000 pieces/mm 2 6000 pieces/mm 2 8000 pieces/mm 2 Or 10000 pieces/mm 2 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, when the holes of the base layer and the conductive layer are staggered, the shortest distance between the holes in the conductive layer and the edges of the holes in the base layer is 1 to 3 μm, for example, 1 μm, 1.5 μm, 2 μm, 2.5 μm, or 3 μm, but the present invention is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
The shortest distance between the edges of the holes in the conductive layer and the holes in the substrate layer is 1-3 mu m when the vertical projection is on the horizontal plane, and the high-extensibility performance of the substrate layer can be better exerted when the distance between the staggered holes is in the range. In addition, the staggered holes are more beneficial to relieving the stress concentration phenomenon of the heterogeneous interface.
Preferably, the average pore density of the substrate layer is 500-10000 pores/mm 2 For example 500 pieces/mm 2 800 pieces/mm 2 1600 pieces/mm 2 2000 pieces/mm 2 6000 pieces/mm 2 Or 10000 pieces/mm 2 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the conductive layer has an average pore density of 1 to 1000 pores/mm 2 For example, 1/mm 2 100 pieces/mm 2 500 pieces/mm 2 600 pieces/mm 2 700 pieces/mm 2 Or 1000/mm 2 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
The composite foil comprises a substrate layer and a conductive layer, wherein the substrate layer and the conductive layer are made of different materials, have different roles and have different positions relative to the electrode active coating, so that the hole depth ratio of the substrate layer and the conductive layer is different, and when the average hole density in the substrate layer is 500-10000 holes/mm 2 Within the range of 1-1000 pores per mm 2 When the range is within the range, the elongation, the peeling force and other performances of the composite foil can be further improved. At the same time, the difference in pore density also allows for a mutual adaptation and balance between heterogeneous media of different elongation and peel force between the conductive layer and the substrate layer, and an easier application of active substances on the surface of the conductive layer. The average pore density in the base layer is greater than that of the conductive layer, so that the quality of the composite foil can be further reduced, and the energy density of the electrode can be improved. The active material may be coated on the surface of the conductive layer to fill the holes of the conductive layer and the base layer in whole or in part, or may not fill the holes of the conductive layer and the base layer, and the filling manner may be set correspondingly as required.
Preferably, the average pore area of the composite foil is 1-80%, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 50%, 60% or 80%, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the average pore area ratio in the substrate layer is 1-30%, for example, 1%, 5%, 10%, 15%, 20%, 25% or 30%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the average pore area in the conductive layer is 20-50%, for example, 20%, 25%, 30%, 35%, 40%, 45% or 50%, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The composite foil comprises the substrate layer and the conductive layer, and the substrate layer and the conductive layer are different in material, different in function and different in position relation with the electrode active coating, so that the average pore area ratio of the substrate layer and the conductive layer is different, and when the average pore area ratio in the substrate layer is 1-30% and the average pore area ratio in the conductive layer is 20-50%, the performances such as the extensibility and the stripping force of the composite foil can be further improved. At the same time, the difference in pore area ratio also allows for a mutual adaptation and balance between the elongation between the conductive layer and the substrate layer to meet heterogeneous media of different elongation, and for easier application of active substances on the conductive layer surface.
Preferably, a regulating layer is arranged between the base layer and the conductive layer.
The adjusting layer is used as a transition layer of the substrate layer and the conductive layer, so that the bonding strength between the substrate layer and the conductive layer can be improved, the out-of-phase interface effect can be reduced, and the performance of the composite foil can be further improved.
Preferably, the conditioning layer includes any one or a combination of at least two of a resin layer, a surface treatment agent, or a coupling agent.
Illustratively, the resin layer includes: at least one of phenols, alkyd, amino, polyesters, epoxy, polyurethanes, acrylic, vinyl, fluoro or cyanate esters, polystyrenes, vinyl acetates, polyamides, polyimides, carbamates, melamine; the surface treatment agent comprises: degreasing agents, rust removers, pickling agents, polishing agents, blackening agents, colorants, phosphating solutions, rust inhibitors, protective agents, polishing agents and the like, wherein the coupling agents comprise: silane coupling agents, titanate coupling agents, aluminate coupling agents, metal composite coupling agents, phosphate coupling agents, borate coupling agents, and the like.
Preferably, the composite foil further comprises a seed layer, which is arranged between the base layer and the conductive layer or between the adjustment layer and the conductive layer.
Preferably, the inner surface of the hole further comprises a seed layer.
The composite foil is also provided with the seed layer, and the seed layer can be distributed on the inner surface of the hole, so that the bonding force between the substrate layer and the conductive layer can be improved, the interface effect can be reduced, the stripping force can be improved, and the composite foil can be used for subsequent electroplating thickening to generate the conductive layer.
Preferably, the seed layer comprises a conductive metal material.
Preferably, the conductive metal material comprises any one of Ni, ti, cu, ag, au, pt, fe, co, cr, W, mo, al, mg, K, na, ca, sr, ba, ge, sb, pb, in or Zn or an alloy of at least two metals. Preferably, the seed layer is obtained by vacuum sputtering.
The seed layer is obtained through vacuum sputtering, and the seed layer formed in a vacuum sputtering mode is uniform and energy-saving.
Preferably, the holes of the adjusting layer correspond to the holes of the basal layer, and the holes of the seed layer correspond to the holes of the conductive layer.
When the composite foil comprises the regulating layer and the seed layer and the pore structure is a staggered pore, the pore structure of the regulating layer corresponds to the basal layer, the pore structure of the seed layer corresponds to the pore structure of the conducting layer, and the specific corresponding relation further plays the roles of the regulating layer and the seed layer, so that the performance of the composite foil is improved.
Preferably, the thickness of the adjustment layer is 1-10 μm, for example, 1 μm, 3 μm, 5 μm, 7 μm, 9 μm or 10 μm, and the thickness of the seed layer is 5nm-2 μm, for example, 5nm, 10nm, 50nm, 100nm, 1 μm, 1.5 μm or 2 μm, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the substrate layer includes any one or a combination of at least two of phenolic compounds, alkyd compounds, amino compounds, polyester compounds, epoxy compounds, polyurethane compounds, acrylic compounds, vinyl compounds, fluorine resins or cyanate compounds, polystyrene compounds, vinyl acetate compounds, polyamide compounds, rubber compounds, polyimide compounds, urethane compounds, melamine compounds, BT resin compounds, ABF resin compounds, polypropylene compounds or polyethylene terephthalate compounds;
preferably, the adjustment layer is made of at least one of thermoplastic polyimide resin, modified epoxy resin, modified acrylic resin, modified polyurethane resin, and modified phenolic resin.
Preferably, the conductive layer comprises any one or a combination of at least two of Ni, ti, cu, ag, au, pt, fe, co, cr, W, mo, al, mg, K, na, ca, sr, ba, ge, sb, pb, in or Zn.
The preparation method of the composite foil comprises the following steps:
s1: forming a seed layer or a regulating layer on one side of the substrate layer;
s2: thickening the seed layer of the basal layer by adopting an electroplating thickening mode;
s3: and (3) preparing holes on the surface of the composite foil in the second step.
Preferably, in S1, the manner of forming the seed layer or the adjustment layer on the surface of the base layer includes one or more of electroless plating, PVD, CVD, evaporation plating, sputtering plating, electroplating, and coating. The surface treatment may be performed on the surface of the underlayer before the seed layer is formed on the surface of the underlayer, and the form of the surface treatment includes corona treatment, plasma treatment, and the like, and is not limited in this respect as long as the surface roughness of the underlayer can be improved.
The method for preparing the holes on the surface of the composite foil includes plating, pressing, etching, ablating, etc., and any method that can prepare the holes on the surface of the composite foil is within the present scheme and is not specifically recited herein. Alternatively, a seed layer may be formed directly on the substrate layer containing the holes, and then the conductive layer may be formed by thickening.
In a second aspect, the present invention provides a pole piece comprising a composite foil as described in the first aspect, and an electrode active material layer disposed on a surface of the composite foil.
In a third aspect, the present invention provides an electrode arrangement comprising a coiled electrode assembly comprising a pole piece according to the second aspect.
Preferably, the electrode device further comprises a first tab and a second tab, and the first tab and the second tab are connected with the composite foil according to the first aspect.
In a fourth aspect, the present invention provides a battery device comprising an electrode device according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the composite foil, the hole structure is arranged, so that the weight of the composite foil is further reduced, and the energy density of the battery is improved.
(2) The invention improves the extensibility by controlling the ratio of the aperture D to the aperture depth H, wherein the ratio of the aperture depth to the aperture depth is controlled within a certain range, and too large ratio can generate stress concentration to reduce the stripping force and the extensibility, so that too small ratio has no obvious effect on the improvement of the stripping force and the extensibility.
(3) When the hole structure penetrates through the substrate layer, and the conductive layer in the composite foil is arranged on one side, the conductive layer is embedded into the hole, so that the stripping force between the conductive layer and the substrate is improved; when the conductive layers are arranged on the two sides of the substrate layer, the seed layers between the holes tightly adhere the conductive layers on the two sides of the substrate layer together, so that the stripping force between the conductive layers and the substrate layer is improved;
(4) According to the invention, the elongation of the composite foil is improved, and the existence of holes enables the pulling resistance in the process of processing and winding the lithium battery to be enhanced, so that the stress concentration is reduced; in addition, dendrite generation is reduced, and lateral growth of lithium dendrite is reduced and risk of piercing the separator is reduced because deposited lithium preferentially deposits in the pores when the pores are present.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a composite foil, which comprises a substrate layer and conductive layers on two sides of the substrate layer, wherein an adjusting layer is further arranged between the substrate layer and the conductive layers, and a seed layer is arranged between the adjusting layer and the conductive layers;
the composite foil has a staggered hole structure, holes arranged on the substrate layer are staggered with holes arranged on the conductive layer, the holes in the substrate layer penetrate through the substrate layer, and the ratio of the hole diameter to the hole depth is D 1 /H 1 =2.5 μm/2.5 μm=1, the holes in the conductive layer penetrate the conductive layer, and the ratio of the hole diameter to the hole depth is D 2 /H 2 =5 μm/5 μm=1; the shortest distance of the hole edge between the through holes in the conductive layer and the through holes in the base layer is 2 μm;
the average pore density of the substrate layer was 60 pores/mm 2 The average pore area ratio was 20%, and the average pore density of the conductive layer was 40 pores/mm 2 The average pore area was 30%;
the thickness of the regulating layer is 2 mu m, holes in the regulating layer correspond to holes of the basal layer in a penetrating way, the thickness of the seed layer is 10nm, and holes in the regulating layer correspond to holes of the conducting layer in a penetrating way;
the base layer comprises phenolic resin, the conductive layer is Cu, the regulating layer comprises modified epoxy resin, and the seed layer is sputtered copper.
Example 2
The embodiment provides a composite foil, which comprises a substrate layer and conductive layers on two sides of the substrate layer, wherein an adjusting layer is further arranged between the substrate layer and the conductive layers, and a seed layer is arranged between the adjusting layer and the conductive layers;
the composite foil has a staggered hole structure, wherein holes arranged on the substrate layer and holes arranged on the conductive layer are staggered, the holes in the substrate layer penetrate through the substrate layer, and the ratio of the hole diameter to the hole depth is D 1 /H 1 The holes in the conductive layer penetrate the conductive layer and the ratio of the hole diameter to the hole depth is D =5 μm/0.1 μm=50 2 /H 2 ＝10μm/0.2μm＝50；
The shortest distance of the hole edge between the through holes in the conductive layer and the through holes in the base layer is 3 μm;
the average pore density of the substrate layer was 600 pores/mm 2 The average pore area ratio was 30%, and the average pore density of the conductive layer was 400 pores/mm 2 The average pore area was 50%;
the thickness of the regulating layer is 2 mu m, holes in the regulating layer correspond to holes of the basal layer in a penetrating way, the thickness of the seed layer is 10nm, and holes in the regulating layer correspond to holes of the conducting layer in a penetrating way;
the base layer comprises phenolic resin, the conductive layer is Cu, the regulating layer comprises modified epoxy resin, and the seed layer is sputtered copper.
Example 3
The embodiment provides a composite foil, which comprises a substrate layer and conductive layers on two sides of the substrate layer, wherein an adjusting layer is further arranged between the substrate layer and the conductive layers, and a seed layer is arranged between the adjusting layer and the conductive layers;
the composite foil has a staggered hole structure, wherein holes arranged on the substrate layer and holes arranged on the conductive layer are staggered, the holes in the substrate layer penetrate through the substrate layer, and the ratio of the hole diameter to the hole depth is D 1 /H 1 =0.1 μm/8 μm=1/80, the holes in the conductive layer penetrate the conductive layer, andthe aperture and the aperture depth ratio are D 2 /H 2 ＝0.1μm/18μm＝1/180；
The shortest distance of the hole edge between the through holes in the conductive layer and the through holes in the base layer is 1 μm;
the average pore density of the substrate layer was 1/mm 2 The average pore area ratio was 2%, and the average pore density of the conductive layer was 1/mm 2 The average pore area was 20%;
the thickness of the regulating layer is 2 mu m, holes in the regulating layer correspond to holes of the basal layer in a penetrating way, the thickness of the seed layer is 10nm, and holes in the regulating layer correspond to holes of the conducting layer in a penetrating way;
the base layer comprises phenolic resin, the conductive layer is Cu, the regulating layer comprises modified epoxy resin, and the seed layer is sputtered copper.
Example 4
This example provides a composite foil that is identical to example 1 except that the hole structures are through holes through the base layer and the conductive layer rather than staggered holes.
Example 5
The embodiment provides a composite foil, which is provided with a blind hole except for a hole structure, is arranged on the surface of a conductive layer and does not penetrate through a substrate layer, and correspondingly, the ratio of the aperture of the blind hole to the depth of the blind hole is D 1 /H 1 ＝2.5μm/2.5μm＝1，D 2 /H 2 =5 μm/4 μm=1.25, and the rest is the same as in example 1.
Example 6
This example provides a composite foil which is the same as example 1 except that the shortest distance of the hole edges between the through holes in the conductive layer and the through holes in the base layer is 0.1 μm.
Example 7
This example provides a composite foil which is the same as example 1 except that the shortest distance of the hole edges between the through holes in the conductive layer and the through holes in the base layer is 4 μm.
Example 8
The implementation isExample provides a composite foil that, in addition to D 1 /H 1 =0.1 μm/15 μm=1/150, and the rest is the same as in example 1.
Example 9
The present embodiment provides a composite foil except for D 1 /H 1 =10 μm/0.1 μm=100, and the rest is the same as in example 1.
Example 10
The present embodiment provides a composite foil except for D 2 /H 2 =0.05 μm/15 μm=1/300, and the rest is the same as in example 1.
Example 11
The present embodiment provides a composite foil except for D 2 /H 2 =12.5 μm/0.1 μm=125, and the rest is the same as in example 1.
Example 12
This implementation provides a composite foil that is identical to example 1, except that no seed layer is provided.
Example 13
This implementation provides a composite foil that is identical to example 1, except that the seed layer and the conditioning layer are not provided.
Comparative example 1
The embodiment provides a composite foil with a ratio of pore diameter to pore depth of D except for the pores 1 /H 1 ＝0.1μm/22.5μm＝1/225，D 2 /H 2 Except for=0.1 μm/22.5 μm=1/225, the rest was the same as in example 1.
Comparative example 2
The embodiment provides a composite foil with a ratio of pore diameter to pore depth of D except for the pores 1 /H 1 ＝12.5μm/0.1μm＝125，D 2 /H 2 Except for 12.5 μm/0.1 μm=125, the rest was the same as in example 1.
The composite foils obtained in the above examples and comparative examples were tested for their peel force, elongation and safety properties after assembled into a battery; the peel force testing method comprises the steps of preparing a spline from the prepared composite foil, stretching the spline on a tensile testing machine according to the direction of 90 degrees, and testing the peel force of the composite foil; the elongation testing method comprises the steps of preparing a spline from the prepared composite foil, stretching the spline on a tensile testing machine, and testing the elongation of the composite foil; the safety performance testing method comprises the following steps: and (3) coating an active layer on the surface of the composite foil to prepare an electrode, assembling the electrode into a lithium ion battery, carrying out cyclic charge and discharge, taking out the electrode after a certain number of cycles, and carrying out electron microscope observation on the surface of the electrode, wherein the current of constant current charge or discharge is 1A-20A and the gradient is 1A.
The test results are shown in the following table:
TABLE 1
From the above table it can be seen that:
the composite foil material obtained by the invention has higher elongation and stripping force, and can improve the safety performance of the battery; as is clear from examples 1 and comparative examples 1 to 2, even if the hole structure is provided on the composite foil, the hole depth ratio is not within the scope of the present invention, the performance of the composite foil cannot be effectively improved; as can be seen from examples 1 and 4-7, the holes of the present invention are preferably staggered holes, and the shortest distance between the edges of the holes is preferably within a specific range, so that the performance of the composite foil can be further improved; from examples 1 and 8 to 11, it is understood that the ratio of the diameter to the depth of the holes in the base layer and the ratio of the diameter to the depth of the holes in the conductive layer need to be within a specific range; as can be seen from examples 1 and 12-13, the arrangement of the seed layer and the common arrangement of the seed layer and the adjustment layer of the present invention can further improve the performance of the foil.
In summary, the invention provides a composite foil and application thereof, wherein the composite foil has a specific depth-to-diameter ratio hole structure, so that the weight of the foil is reduced, the energy density is improved, the elongation and the peeling force of the foil are also improved, the elongation is improved, the stress concentration is avoided, and the safety performance of a battery is improved; meanwhile, the risk that lithium dendrites pierce through the membrane is reduced due to the arrangement of the pore structure, so that the safety performance of the battery is further improved.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The composite foil is characterized by comprising a substrate layer and a conductive layer on at least one side surface of the substrate layer, wherein the composite foil is provided with a hole structure, the ratio of the aperture of the hole to the depth of the hole is 1/200-110, D is the aperture, and H is the depth of the hole.
2. The composite foil of claim 1, wherein the ratio of pore diameter to pore depth of the pores is 1/200 ∈d/H ∈100;
preferably, the H is 0.1-20 μm.
3. The composite foil according to claim 1 or 2, wherein the ratio of pore diameter to pore depth of the pores in the substrate layer is 1/80.ltoreq.d 1 /H 1 Less than or equal to 50, wherein D 1 For the aperture of the holes in the substrate layer, H 1 The hole depth of the holes in the basal layer;
preferably, in the conductive layer, the ratio of the pore diameter to the pore depth of the pores is 1/200.ltoreq.D 2 /H 2 Less than or equal to 80, wherein D 2 Is the pore diameter of the pores in the conductive layer, H 2 The hole depth of the holes in the conductive layer;
preferably H 1 0.1-8 μm;
preferably H 2 0.1-18 μm.
4. A composite foil according to claim 3, wherein the holes in the base layer and the holes in the conductive layer are staggered;
preferably, the holes in the base layer and the conductive layer are independently through holes and/or blind holes, respectively.
5. The composite foil according to claim 4, wherein the shortest distance between the holes in the conductive layer and the holes in the base layer is 1-3 μm at the hole edge;
preferably, the composite foil has an average pore density of 1-10000 pores/mm 2 ；
Preferably, the average pore density of the substrate layer is 500-10000 pores/mm 2 ；
Preferably, the conductive layer has an average pore density of 1 to 1000 pores/mm 2 ；
Preferably, the composite foil has an average pore area ratio of 1-80%, preferably 1-60%;
preferably, the average pore area of the substrate layer is 1-30%;
preferably, the conductive layer has an average pore area of 20-50%.
6. The composite foil according to any one of claims 1-5, wherein an adjustment layer is provided between the base layer and the conductive layer;
preferably, the conditioning layer comprises any one or a combination of at least two of a resin layer, a surface treatment agent or a coupling agent;
preferably, the composite foil further comprises a seed layer, which is arranged between the base layer and the conductive layer or between the adjustment layer and the conductive layer;
preferably, the inner surface of the hole further comprises a seed layer;
preferably, the seed layer comprises a conductive metal material;
preferably, the seed layer is obtained by vacuum sputtering.
7. A pole piece, characterized in that it comprises a composite foil as claimed in any one of claims 1-6, and an electrode active material layer arranged on the surface of the composite foil.
8. An electrode assembly comprising a rolled electrode assembly comprising the pole piece of claim 7.
9. The electrode assembly of claim 8, further comprising a first tab and a second tab, the first tab and the second tab being connected to the composite foil of any one of claims 1-6.
10. A battery device, characterized in that it comprises an electrode device according to claim 8 or 9.
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