WO2024254743A1 - 电化学装置及包含其的用电设备 - Google Patents

电化学装置及包含其的用电设备 Download PDF

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Publication number
WO2024254743A1
WO2024254743A1 PCT/CN2023/099742 CN2023099742W WO2024254743A1 WO 2024254743 A1 WO2024254743 A1 WO 2024254743A1 CN 2023099742 W CN2023099742 W CN 2023099742W WO 2024254743 A1 WO2024254743 A1 WO 2024254743A1
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Prior art keywords
electrochemical device
layer
electrode assembly
coating
insulating layer
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Ceased
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PCT/CN2023/099742
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English (en)
French (fr)
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WO2024254743A9 (zh
Inventor
江南
曾巧
闫东阳
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to EP23940981.6A priority Critical patent/EP4726819A1/en
Priority to PCT/CN2023/099742 priority patent/WO2024254743A1/zh
Priority to CN202380034178.5A priority patent/CN118985059A/zh
Publication of WO2024254743A1 publication Critical patent/WO2024254743A1/zh
Priority to US19/417,533 priority patent/US20260100482A1/en
Anticipated expiration legal-status Critical
Publication of WO2024254743A9 publication Critical patent/WO2024254743A9/zh
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • H01M10/0587Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/102Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105Pouches or flexible bags
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/443Particulate material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/446Composite material consisting of a mixture of organic and inorganic materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/449Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/449Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46Separators, membranes or diaphragms characterised by their combination with electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the gap between two adjacent first coating layers is reserved for electrolyte transmission, which improves the electrolyte infiltration effect, improves the problem of lithium deposition on the electrode caused by poor electrolyte infiltration, and improves the cycle performance. Therefore, the electrochemical device of the present application has high cyclability while maintaining safety.
  • the first coating is in a strip shape
  • the substrate layer includes two sides opposite to each other in a second direction perpendicular to the first direction
  • the first coatings are arranged obliquely relative to the sides. Therefore, the bonding force between the first coating and the adjacent electrode sheets is continuously distributed on each edge of the electrode assembly, thereby improving the ability of the electrode assembly to resist deformation and improving the cycle performance.
  • the angle between the first coating and the side when viewed along the first direction, is ⁇ 1 , 25° ⁇ 1 ⁇ 65°.
  • the angle ⁇ 1 is within this range, the adhesion between the first coating and the edge of the pole piece can be maintained, and the edge deformation of the pole piece can be suppressed, thereby improving the cycle performance.
  • the electrochemical device also includes a first metal plate and a second metal plate, both of which are connected to the electrode assembly; in a third direction perpendicular to the first direction, the electrode assembly also includes a second end face opposite to the first end face, and the first metal plate and the second metal plate extend out of the electrode assembly from the second end face.
  • the present application also provides an electrical equipment, comprising any of the above-mentioned electrochemical devices.
  • FIG1 is a first direction view of an electrochemical device provided by an embodiment of the present application.
  • FIG3 is a first direction view of the electrode assembly shown in FIG2 as viewed from the side where the second surface is located;
  • FIG4 is a second direction view of the electrode assembly shown in FIG2;
  • FIG5 is a cross-sectional view of the electrode assembly shown in FIG2 along line V-V;
  • FIG6 is a cross-sectional view of the electrode assembly shown in FIG4 along line VI-VI;
  • FIG. 7 is a first direction view of the first isolation film of the electrode assembly shown in FIG. 6 from a side close to the first surface of the electrode assembly;
  • FIG8 is a first direction view of the first isolation film shown in FIG7 from the side close to the second surface of the electrode assembly;
  • FIG10 is a second direction view of an electrode assembly provided by another embodiment of the present application.
  • an electrochemical device includes any device that generates an electrochemical reaction, and its specific examples include all kinds of primary batteries, secondary batteries, fuel cells, solar cells or capacitors.
  • the electrochemical device is a lithium secondary battery, which may include a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery.
  • an embodiment of the present application provides an electrochemical device 100, comprising a housing 10, an electrode assembly 20 (shown in FIG. 2 and FIG. 3 ) contained in the housing 10, an electrolyte, a first metal plate 30, and a second metal plate 40.
  • the housing 10 is a metal housing, such as a steel housing or an aluminum housing.
  • the housing 10 is a packaging bag obtained by packaging with a packaging film, that is, the electrochemical device 100 can be a soft-pack battery.
  • FIG. 2 and FIG. 3 show that the electrochemical device 100 includes an electrode assembly 20.
  • the electrochemical device 100 includes a plurality of electrode assemblies 20.
  • the electrode assembly 20 includes a plurality of electrode sheets and a first isolation film 23 disposed between the plurality of electrode sheets.
  • the plurality of electrode sheets are stacked along a first direction Z to form a stacked structure.
  • the first direction Z refers to the thickness direction of the electrode assembly 20.
  • the plurality of pole pieces include a first pole piece 21 and a second pole piece 22 with opposite polarities.
  • the first isolation film 23 is disposed between adjacent first pole pieces 21 and second pole pieces 22 to reduce the risk of a short circuit caused by direct contact between the first pole piece 21 and the second pole piece 22.
  • the first isolation film 23 includes at least one first portion 23a disposed in a plurality of pole pieces.
  • the first isolation film 23 includes a plurality of first portions 23a, each of which is used to separate adjacent first pole pieces 21 and second pole pieces 22.
  • the plurality of first portions 23a are disposed separately, that is, the plurality of first portions 23a are configured as independent diaphragms.
  • the electrode assembly 20 is obtained by alternately stacking the first pole piece 21, the first portion 23a, and the second pole piece 22.
  • the edge of the first portion 23a of the first isolation film 23 exceeds the edge of the pole piece in both the third direction X and the second direction Y to separate the adjacent first pole piece 21 and the second pole piece 22.
  • the end faces of the first portion 23a of the first isolation film 23 on both sides of the second direction Y are respectively used as the second end face 203 and the first end face 204
  • the end faces of the first portion 23a of the first isolation film 23 on both sides of the third direction X are respectively used as the first side face 205 and the second side face 206.
  • the third insulating layer 70 is generally in the form of a sheet, and covers at least a portion of the first surface 201, at least a portion of the second surface 202, and at least a portion of the second side surface 206, and is connected to the first surface 201, the second surface 202, and the second side surface 206.
  • the third insulating layer 70 constrains the electrode assembly 20 in the first direction Z and the third direction X, and reduces the risk of shrinking the end of the first portion 23a of the first isolation film 23 close to the second side surface 206 in the third direction X.
  • the first insulating layer 50, the fourth insulating layer 60, the third insulating layer 70 and the second insulating layer 80 are all adhesive and bonded to the electrode assembly 20.
  • the materials of the first insulating layer 50, the fourth insulating layer 60, the third insulating layer 70 and the second insulating layer 80 can be single-sided adhesive or double-sided adhesive.
  • the first coating 232 includes a first inorganic particle layer 232a and a first bonding layer 232b which are stacked.
  • the first inorganic particle layer 232a is connected to the substrate layer 231, and the first bonding layer 232b is arranged on the surface of the first inorganic particle layer 232a away from the substrate layer 231, and the first isolation film 23 is bonded to the adjacent pole piece through the first bonding layer 232b.
  • the first bonding layer 232b can bond the pole piece, improve the interfacial bonding force between the first isolation film 23 and the pole piece, reduce the expansion deformation when the electrochemical device 100 produces gas, that is, improve the anti-deformation ability of the electrochemical device 100, reduce the risk of deformation and structural damage of the electrode assembly 20, and thus improve the cycle performance of the electrochemical device 100.
  • the first coating layer 232 is disposed on the surface of the substrate layer 231 in a strip shape. And a plurality of first coatings 232 are arranged parallel to each other.
  • the substrate layer 231 includes two side edges 231a opposite to each other in the second direction Y.
  • the angle between the first coating 232 and the side edge 231a is ⁇ 1 .
  • the first coating 232 is arranged obliquely relative to the side edge 231a, that is, 0° ⁇ 1 ⁇ 90°, so the bonding force between the first coating 232 and the pole piece is continuously distributed on the edge of the electrode assembly in the second direction Y and the third direction X, thereby improving the ability of the electrode assembly to resist deformation and improving the cycle performance.
  • 25° ⁇ 1 ⁇ 65° so as to maintain the bonding force between the first coating 232 and the edge of the pole piece, curb the edge deformation of the pole piece, and thus improve the cycle performance.
  • ⁇ 1 ⁇ 25° since the first coating 232 is relatively flush with the third direction X, the adhesion between the first isolation film 23 and the pole piece in the second direction Y may be reduced, resulting in the edge of the electrode assembly 20 in the third direction X may be deformed, affecting the cycle life.
  • the width of the first coating 232 is D 1
  • the distance between two adjacent first coatings 232 is D 2
  • D 1 and D 2 satisfy: 0.3D 2 ⁇ D 1 ⁇ 0.5D 2 .
  • D 1 >0.5D 2 under the condition of a certain area of the electrode, D 2 is small, so that the space available for electrolyte transmission is reduced, and poor electrolyte infiltration causes lithium precipitation problems on the electrode, affecting the cycle performance.
  • D 1 ⁇ 0.3D 2 the bonding area between the first coating 232 and the electrode is reduced, the bonding force is reduced, and the anti-deformation ability is correspondingly reduced, affecting the cycle performance.
  • the first adhesive layer 232b and the second adhesive layer 233b both include adhesive materials, and the adhesive materials include at least one of the following polymers: copolymers of vinylidene fluoride and hexafluoropropylene, copolymers of vinylidene fluoride and trichloroethylene, polymethyl methacrylate, polyacrylic acid, polyacrylic acid salt, polyacrylonitrile, polyvinyl pyrrolidone, polyvinyl acetate, copolymers of ethylene-vinyl acetate, polyimide, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl amylopectin, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, amylopectin, sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, copolymers of acrylonitrile-styrene-but
  • the first coating 232 and the second coating 233 intersect at different planes, and the angle between the first coating 232 and the second coating 233 is ⁇ 3 , 0° ⁇ 3 ⁇ 180°.
  • the gaps G 1 between the multiple first coatings 232 and the gaps G 2 between the multiple second coatings 233 are staggered to further improve the electrolyte infiltration effect.
  • the first coating 232 and the second coating 233 can also be arranged in parallel, in which case the angle ⁇ 1 between the first coating 232 and the side 231a is equal to the angle ⁇ 2 between the second coating 233 and the side 231a.
  • each first coating layer 232 or each second coating layer 233 may be intermittently arranged, such as being arranged in a plurality of blocks or a plurality of islands on the surface of the substrate layer 231.
  • the angle ⁇ 1 between the first coating layer 232 and the side 231a is the angle between the line connecting the plurality of blocks or the plurality of islands and the side 231a
  • the angle ⁇ 2 between the second coating layer 233 and the side 231a is the angle between the line connecting the plurality of blocks or the plurality of islands and the side 231a.
  • each intermittently arranged first coating layer 232 or each intermittently arranged second coating layer 233 is also provided with a gap G3 , which can be used as a channel for electrolyte transmission, further improving the electrolyte transmission performance.
  • the first isolation film 23 further includes a second portion 23b and a third portion 23c located outside the plurality of pole pieces and opposite to each other in the first direction Z, wherein the surface of the second portion 23b facing away from the pole piece is connected to the first insulating layer as the first surface 201 of the electrode assembly 20, and the surface of the third portion 23c facing away from the pole piece is connected to the first insulating layer as the second surface 202 of the electrode assembly 20.
  • the plurality of first portions 23a, the second portion 23b and the third portion 23c of the first isolation film 23 are configured as a whole and form a winding structure, and the plurality of pole pieces are located in the winding structure.
  • the first isolation film 23 is wound around the second direction Y with one end as the center to form a winding structure with each n pole pieces, wherein n is an integer greater than or equal to 1. That is, n pole pieces are arranged between each two adjacent first portions 23a.
  • FIG. 11 shows that three pole pieces are arranged between two adjacent first portions 23a.
  • a second isolation film 24 is also arranged between the plurality of pole pieces between the two adjacent first portions 23a.
  • the second isolation film 24 is made of insulating material to prevent the multiple pole pieces between two adjacent first parts 23a from directly contacting and short-circuiting.
  • the material of the second isolation film 24 may include at least one of polyolefin, polyvinylidene fluoride, polyethylene terephthalate, cellulose, polyimide, polyamide, spandex or polyphenylene phthalide.
  • the first isolation film 23 which is provided as an integral part is configured as a winding structure.
  • the first isolation film 23 as a whole binds a plurality of pole pieces in the first direction Z and the third direction X, and there is no need to additionally configure a second insulating layer and a third insulating layer which bind the electrode assembly 20 in the first direction Z and the third direction X.
  • the first isolation film 23 which is configured as a winding structure has a weaker binding on the edge of the pole piece in the third direction X, which is beneficial for the electrolyte to flow through the edge of the pole piece in the third direction X and fully infiltrate the pole piece.
  • the first isolation film 23 includes a second portion 23b and a third portion 23c which are located outside the plurality of pole pieces, and the first insulating layer 50 is connected to the second portion 23b and the third portion 23c of the first isolation film 23.
  • the surface roughness of the first isolation film 23 is greater than the surface roughness of the current collector of the pole piece, which increases the bonding between the first insulating layer 50 and the electrode assembly 20. force, reducing the risk of the first insulating layer 50 falling off.
  • an embodiment of the present application further provides an electric device 1, and the electric device 1 includes the above electrochemical device 100.
  • the electric device 1 of the present application can be, but not limited to, a laptop computer, a pen-input computer, a mobile computer, an electronic book player, a portable phone, a portable fax machine, a portable copier, a portable printer, a head-mounted stereo headset, a video recorder, an LCD TV, a portable cleaner, a portable CD player, a mini CD, a transceiver, an electronic notepad, a calculator, a memory card, a portable recorder, a radio, a backup electronic source, a motor, a car, a motorcycle, a power bicycle, a bicycle, a lighting fixture, a toy, a game console, a clock, an electric tool, a flashlight, a camera, a large household battery and a lithium ion capacitor, etc.
  • the present application is described in detail below through specific embodiments and comparative examples. Among them, the present application is described by taking the electrochemical device as a soft-pack battery as an example and combining the specific preparation process and testing method. Those skilled in the art should understand that the preparation method described in the present application is only an example, and any other suitable preparation method is within the scope of the present application.
  • the slurry formed by mixing the inorganic particle material and the binder is coated on the surface of the substrate layer at intervals to form a plurality of first inorganic particle layers arranged at intervals, and then the binder is coated on the surface of the plurality of first inorganic particle layers to form a plurality of first bonding layers to obtain a plurality of first coating layers arranged at intervals, and then the slurry formed by mixing the inorganic particle material and the binder is coated on the other surface of the substrate layer at intervals to form a plurality of second inorganic particle layers arranged at intervals, and then the binder is coated on the surface of the plurality of second inorganic particle layers to form a plurality of second bonding layers to obtain a plurality of second coating layers arranged at intervals, thereby obtaining a first isolation film.
  • the first isolation film and a plurality of pole pieces are stacked to obtain an electrode assembly, wherein the first isolation film has a winding structure, three pole pieces are arranged between the first parts of two adjacent first isolation films, and the surfaces of the second and third parts of the first isolation film away from the pole pieces serve as the first surface and the second surface of the electrode assembly.
  • the first surface, the second surface and the second end surface of the assembly, wherein the relationship between the width W 2 of the first insulating layer and the width W 1 of the electrode assembly is: W 2 0.8W 1 .
  • the electrode assembly and the electrolyte are packaged in an aluminum-plastic film to obtain an electrochemical device.
  • the difference from the first embodiment is that at least one of the value of D 1 /D 2 , the value of W 2 /W 1 , and the value of the angle ⁇ 1 is different.
  • Example 1 The difference from Example 1 is that the slurry is continuously coated on the surface of the substrate layer to form the first inorganic particle layer and the second inorganic particle layer, and the slurry is continuously coated on the surface of the first inorganic particle layer and the surface of the second inorganic particle layer to form the first bonding layer. That is, the plurality of first coating layers and the plurality of second coating layers spaced apart in Example 1 are connected as one.
  • the electrochemical devices of Comparative Example 1 and Examples 1-10, 12-13 were subjected to cycle tests, and the test results are recorded in Table 1.
  • the cycle test steps include: charging the electrochemical device to 4.43V at a constant current of 1C at 45 degrees Celsius, then charging to 0.05C at a constant voltage, then standing for 5 minutes, and then discharging to 3.0V at 0.7C.
  • the discharge capacity at this time is measured by a commercially available battery performance tester as the first discharge capacity of the electrochemical device, which is calculated as 100%; the above charge and discharge steps are cycled for 1000 times in sequence, and the ratio of the discharge capacity of the electrochemical device after the cycle to the first capacity multiplied by 100% is the capacity retention rate; the electrochemical device is fully charged according to the charging process, and the negative electrode plate interface and lithium precipitation are disassembled to observe.
  • Comparing Comparative Example 1 with Examples 1-10, 12-13 it can be seen that when a first insulating layer with a wide width is used to constrain the electrode assembly in the first direction, when the first coating and the second coating are continuously coated on the two surfaces of the substrate layer, it will cause serious electrolyte infiltration. A large amount of purple spot lithium precipitation will be generated in the main area of the pole piece (the area close to the center of the pole piece), affecting the life of the electrochemical device; and when the first coating and the second coating are intermittently coated on the two surfaces of the substrate layer, the gap between the adjacent first coating and the adjacent second coating is reserved for electrolyte transmission, improving the electrolyte infiltration effect and the life of the electrochemical device. Therefore, the cycle capacity retention rate of Comparative Example 1 is the lowest.
  • the electrochemical devices of Comparative Example 1 and Examples 2 and 14 were subjected to a hot box test, and the test results are recorded in Table 2.
  • the steps of the hot box test include: charging the electrochemical device to 4.43V at a constant current of 0.2C at 25 ⁇ 5°C, and then charging to 0.01C at a constant voltage.
  • the electrochemical device was heated to 140 ⁇ 2°C at a rate of 5 ⁇ 2°C/min, and then maintained for 60 minutes. The electrochemical device was observed to see if there were any failure phenomena such as fire and explosion. If not, the hot box test was passed, otherwise it was not passed.
  • the hot box test pass rate of 20 electrochemical devices was counted. After the test, the electrochemical device was disassembled to observe whether the diaphragm shrank.
  • the electrochemical devices of Examples 1-6, 9, and 11 were subjected to a drop test, and the test results are recorded in Table 3.
  • the drop test steps include: charging the electrochemical device to 4.43V at a constant current of 0.2C at 25 ⁇ 5°C, and then charging to 0.01C at a constant voltage.
  • the electrochemical device is fixed in the drop test fixture and dropped 6 times in sequence on the 6 sides of the drop test fixture at a height of 1.8m. After each drop, observe whether the electrochemical device is damaged and measure the open circuit voltage of the electrochemical device. If the voltage is less than 3.0V, the electrochemical device is judged to have failed. If there is no damage and the open circuit voltage is higher than 3.0V, it is judged to have not failed. Continue the test until failure, and record the number of drops when the electrochemical device fails. Then disassemble and analyze the electrochemical device to observe whether the diaphragm shrinks.
  • Example 11 Comparing Examples 2, 4-6, and 11, it can be seen that when 0.7W 1 ⁇ W 2 is satisfied, the electrochemical device has more drop times and better drop resistance. In Example 11, W 2 is too small, and failure caused by shrinkage of the first isolation film occurs during the drop process, resulting in the least drop times and the worst drop resistance.

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Abstract

一种电化学装置及包含其的用电设备。电化学装置包括壳体、电极组件、第一绝缘层和电解液,电极组件和电解液收容于壳体中。电极组件包括沿第一方向堆叠的多个极片和配置在多个极片之间的第一隔离膜。电极组件还包括在第一方向上相对的第一表面和第二表面以及连接于第一表面和第二表面之间的第一端面。第一绝缘层与第一表面、第二表面和第一端面均相粘接。第一隔离膜包括基材层和间隔设置于基材层面向相邻的极片的表面第一涂层。

Description

电化学装置及包含其的用电设备 技术领域
本申请涉及储能装置领域,尤其是涉及一种电化学装置及包含其的用电设备。
背景技术
电化学装置(例如锂离子电池)由于具备能量密度大、输出功率高、循环寿命长和环境污染小等优点而被广泛应用于电动汽车以及消费类电子产品中。然而电化学装置在受到挤压、碰撞或穿刺等异常情况时有可能发生着火等安全问题。
发明内容
本申请的一个目的在于提出一种电池,其具有较好的循环性能以及可降低电化学装置发生内短路的风险。
本申请提供一种电化学装置,包括壳体、电极组件、第一绝缘层和电解液,电极组件和电解液收容于所述壳体内。电极组件包括沿第一方向堆叠的多个极片和配置在多个极片之间的第一隔离膜。电极组件还包括在第一方向上相对的第一表面和第二表面以及连接于第一表面和第二表面之间的第一端面。第一绝缘层与第一表面、第二表面和第一端面均相粘接。第一隔离膜包括基材层和间隔设置于基材层面向相邻的极片的表面的第一涂层。
本申请设置连接电极组件的第一表面、第二表面和第一端面的第一绝缘层,第一绝缘层在第一方向上束缚电极组件,降低第一隔离膜收缩导致的内短路风险,提高安全性能。然而,采用第一绝缘层在第一方向上束缚电极组件,可能使第一隔离膜与相邻极片之间的间隙减小,从而使得可供电解液传输的空间减小,电解液浸润不良。本申请设置第一隔离膜包括多个间隔设置的第一 涂层,相邻两个第一涂层之间的间隙为电解液传输预留空间,提高电解液浸润效果,改善因电解液浸润不良而引发的极片析锂问题,提高循环性能。因此,本申请的电化学装置在维持安全性的前提下具有高循环性。
在一些可能的实现方式中,第一涂层呈条状,基材层包括在与第一方向垂直的第二方向上相对的两个侧边,多个第一涂层相对侧边倾斜设置。因此,第一涂层与相邻极片之间的粘接力在电极组件的各个边缘上连续分布,提高电极组件抗变形的能力,改善循环性能。
在一些可能的实现方式中,沿第一方向观察时,第一涂层与侧边的夹角为θ1,25°≤θ1≤65°。在夹角θ1处于该范围时,可以保持第一涂层与极片边缘的粘接力,遏制极片的边缘变形,从而提高循环性能。
在一些可能的实现方式中,沿第一方向观察时,第一涂层的宽度为D1,相邻的两个第一涂层之间的间距为D2,0.3D2≤D1≤0.5D2。当D1>0.5D2时,在极片面积一定的情况下,D2较小,使得可供电解液传输的空间减小,电解液浸润不良使极片析锂问题恶化,影响循环性能;当D1<0.3D2时,第一涂层与极片之间的粘接面积减小,粘结力降低,抗变形能力也相应降低,影响循环性能。
在一些可能的实现方式中,第一隔离膜还包括多个第二涂层,多个第二涂层间隔设置于基材层背离多个第一涂层的表面。相邻的相邻两个第二涂层之间的间隙为电解液传输预留空间,提高电解液浸润效果,进一步改善因电解液浸润不良而引发的极片析锂问题,提高循环性能。
在一些可能的实现方式中,第一涂层和第二涂层异面相交,如此相邻两个第一涂层之间的间隙和相邻两个第二涂层之间的间隙交错设置,进一步提高电解液浸润效果,进一步改善因电解液浸润不良而引发的极片析锂问题,提高循环性能。
在一些可能的实现方式中,第一隔离膜还包括位于多个极片中的多个第一部分以及位于多个极片外并在第一方向上相对的第二部分和第三部分,每个第一部分配置于相邻的两个极片之间,多个第一部分、第二部分和第三部分配置为一体并形成卷绕结构。第一隔离膜配置为卷绕结构,在多个不同的方向上束缚多个极片,无需配置额外的绝缘层以在特定的方向上束缚多个极片。再者,第一绝缘层与第一隔离膜的第二部分和第三部分连接,增大第一绝缘层与电极组件之间的粘结力,降低第一绝缘层脱落的风险,进而降低第一隔离膜收缩引发内短路的风险。
在一些可能的实现方式中,在与第一方向和第二方向均垂直的第三方向上,电极组件的宽度为W1,第一绝缘层的宽度为W2,0.7W1≤W2≤W1。在电极组件的宽度W1和第一绝缘层的宽度W2处于该范围时,可以保持第一绝缘层与第一端面的粘接力,降低第一隔离膜收缩引发内短路的风险,提高安全性能。
在一些可能的实现方式中,0.7W1≤W2≤0.95W1。在一些可能的实现方式中,0.85W1≤W2≤0.95W1
在一些可能的实现方式中,第一涂层包括第一无机颗粒层和第一粘接层,第一无机颗粒层与基材层相接,粘接层设置于无机颗粒层背离基材层的表面并与相邻的极片粘接。第一粘接层与极片粘接,提高第一隔离膜与极片的界面粘结力,减少电化学装置内部产气时的膨胀变形,改善循环性能。
在一些可能的实现方式中,第一涂层包括无机颗粒和粘结剂。
在一些可能的实现方式中,电化学装置还包括第二绝缘层,电极组件还包括连接于第一表面和第二表面之间的第二端面,定义电极组件的长度方向为第二方向,第一表面和第二表面在第二方向上相对,第二绝缘层与第一表面、第二表面和第二端面均相连接。设置连接电极组件的第一表面、第二表面和第二端面的第二绝缘层,降低第一隔离膜靠近第二端面的一端收缩导致内短路的风险。
在一些可能的实现方式中,第一绝缘层为单面胶或双面胶。
在一些可能的实现方式中,第二绝缘层为单面胶或双面胶。
在一些可能的实现方式中,电化学装置还包括第一金属板和第二金属板,第一金属板和第二金属板均与电极组件连接;在与第一方向垂直的第三方向上,电极组件还包括与第一端面相对的第二端面,第一金属板和第二金属板从第二端面伸出电极组件。
在一些可能的实现方式中,壳体为包装袋。
本申请还提供一种用电设备,包括上述任一种电化学装置。
附图说明
本申请的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解,其中:
图1为本申请一实施例提供的电化学装置的第一方向视图;
图2为图1所示的电化学装置的电极组件自第一表面所在的一侧观察的第一方向视图;
图3为图2所示的电极组件自第二表面所在的一侧观察的第一方向视图;
图4为图2所示的电极组件的第二方向视图;
图5为图2所示的电极组件沿V-V的剖视图;
图6为图4所示的电极组件沿VI-VI的剖视图;
图7为图6所示的电极组件的第一隔离膜自靠近电极组件的第一表面所在的一侧的第一方向视图;
图8为图7所示的第一隔离膜自靠近电极组件的第二表面所在的一侧的第一方向视图;
图9为本申请另一实施例提供的第一隔离膜的第一方向视图;
图10为本申请另一实施例提供的电极组件的第二方向视图;
图11为本申请又一实施例提供的电极组件的第二方向视图;
图12为本申请一实施例提供的用电设备的结构示意图。
主要元件符号说明
电化学装置                    100
壳体                          10
电极组件                      20
第一金属板                    30
第二金属板                    40
第一隔离膜                    23
第一极片                      21
第二极片                      22
第一集流体                    211
第一活性物质层                212
第二集流体                    221
第二活性物质层                222
第一表面                      201
第二表面                      202
第二端面                      203
第一端面                      204
第一侧面                      205
第二侧面                      206
第一绝缘层                    50
第四绝缘层                    60
第三绝缘层                    70
第二绝缘层                    80
基材层                        231
第一涂层                      232
间隙                          G1、G2、G3
第一无机颗粒层                232a
第一粘接层                    232b
侧边                           231a
第二涂层                       233
第二无机颗粒层                 233a
第二粘接层                     233b
第二部分                       23b
第三部分                       23c
第二隔离膜                     24
用电设备                       1
第一方向                       Z
第二方向                       Y
第三方向                       X
具体实施方式
下面对本申请实施例中的技术方案进行清楚、详细地描述,显然,所描述的实施例是本申请一部分实施例,而不是全部的实施例。除非另有定义,本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本申请。
下文,将详细地描述本申请的实施方式。但是,本申请可体现为许多不同的形式,并且不应解释为限于本文阐释的示例性实施方式。而是,提供这些示例性实施方式,从而使本申请透彻的和详细的向本领域技术人员传达。
另外,为了简洁和清楚,在附图中,各种组件、层的尺寸或厚度可被放大。遍及全文,相同的数值指相同的要素。另外,应当理解,当要素A被称为“连接”要素B时,要素A可直接连接至要素B,或可能存在中间要素C并且要素A和要素B可彼此间接连接。
进一步,当描述本申请的实施方式时使用“可”指“本申请的 一个或多个实施方式”。
本文使用的专业术语是为了描述具体实施方式的目的并且不旨在限制本申请。如本文所使用,单数形式旨在也包括复数形式,除非上下文另外明确指出。应理解,术语“包括”,当在本说明书中使用时,指存在叙述的特征、数值、步骤、操作、要素和/或组分,但是不排除存在或增加一个或多个其他特征、数值、步骤、操作、要素、组分和/或其组合。应理解,尽管术语第一、第二、第三等可在本文用于描述各种要素、组分、区域、层和/或部分,但是这些要素、组分、区域、层和/或部分不应受这些术语的限制。这些术语用于区分一个要素、组分、区域、层或部分与另一要素、组分、区域、层或部分。因此,下面讨论的第一要素、组分、区域、层或部分可称为第二要素、组分、区域、层或部分,而不背离示例性实施方式的教导。
本申请中的“多个”指的是两个及以上。
在本申请中,电化学装置包括发生电化学反应的任何装置,它的具体实例包括所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容器。示例性的,电化学装置为锂二次电池,该锂二次电池可以包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。
请参阅图1,本申请一实施方式提供一种电化学装置100,包括壳体10、容纳于壳体10中的电极组件20(在图2、图3中示出)和电解液、第一金属板30和第二金属板40。在一些实施例中,壳体10为金属壳体,例如为钢壳或铝壳等。在另一些实施例中,壳体10为采用封装膜封装得到的包装袋,即电化学装置100可以为软包电池。图2和图3示出电化学装置100包括一个电极组件20。在另一些实施例中,为了实现高电压输出,电化学装置100包括多个电极组件20。
如图4所示,电极组件20包括多个极片和配置在多个极片之间的第一隔离膜23。多个极片沿第一方向Z堆叠形成叠片结 构。本实施方式中,第一方向Z指的是电极组件20的厚度方向。多个极片包括极性相反的第一极片21和第二极片22。第一隔离膜23配置于相邻的第一极片21和第二极片22之间,用于降低第一极片21和第二极片22直接接触短路的风险。
第一金属板30和第二金属板40分别电连接于电极组件20,并从壳体10伸出以连接外部元件(图未示)。具体地,第一极片21包括第一集流体211和第一活性物质层212,第一活性物质层212设置于第一集流体211的至少一个表面,第一金属板30电连接于第一集流体211。第二极片22包括第二集流体221和第二活性物质层222,第二活性物质层222设置于第二集流体221的至少一个表面,第二金属板40电连接于第二集流体221。
在一些实施例中,第一极片21为正极极片,第二极片22为负极极片。具体地,第一集流体211、包括Ni、Ti、Cu、Ag、Au、Pt、Fe、Al及其组合物中的至少一种,第一活性物质层212包括正极活性物质,正极活性物质可包括钴酸锂、锰酸锂、镍酸锂、镍钴锰酸锂、磷酸铁锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、富锂锰基材料、镍钴铝酸锂及其组合物中的至少一种。第二集流体221包括Ni、Ti、Cu、Ag、Au、Pt、Fe、Al及其组合物中的至少一种。第二活性物质层222包括负极活性物质,负极活性物质可选自石墨类材料、合金类材料、锂金属及其合金中的至少一种。石墨类材料可选自人造石墨、天然石墨中的至少一种;合金类材料可选自硅、氧化硅、锡、硫化钛中的至少一种。
请参阅图2至图4,电极组件20还包括第一表面201、第二表面202、第二端面203、第一端面204、第一侧面205和第二侧面206。第一表面201和第二表面202在第一方向Z上相对。其中,在第一方向Z上,多个极片中位于最外侧的两个极片的表面分别作为第一表面201和第二表面202。在一些实施例中,多个极片中位于最外侧的两个极片的集流体的表面作为第一表面201和第二表面202。第二端面203和第一端面204在第二方向Y上 相对,并连接于第一表面201和第二表面202之间。第一金属板30和第二金属板40自第二端面203伸出。第一金属板30和第二金属板40可以直接伸出壳体10,也可以转接另一金属板,该另一金属伸出壳体10。第一侧面205和第二侧面206在第三方向X上相对,并连接于第一表面201和第二表面202之间。本申请中,第三方向X指的是电极组件20的宽度方向,第二方向Y指的是电极组件20的长度方向,其中第二方向Y也为第一金属板30和第二金属板40伸出的方向,且第一方向Z、第三方向X和第二方向Y相互垂直。
第一隔离膜23包括设置于多个极片中的至少一第一部分23a。在一些实施例中,第一隔离膜23包括多个第一部分23a,每个第一部分23a用于分隔相邻的第一极片21和第二极片22。多个第一部分23a分体设置,即多个第一部分23a配置为独立的隔膜。此时,电极组件20由第一极片21、第一部分23a和第二极片22交替层叠后得到。第一隔离膜23的第一部分23a的边缘在第三方向X和第二方向Y上均超出极片的边缘,以将相邻的第一极片21和第二极片22隔离开。其中,第一隔离膜23的第一部分23a在第二方向Y的两侧的端面分别作为第二端面203和第一端面204,第一隔离膜23的第一部分23a在第三方向X的两侧的端面分别作为第一侧面205和第二侧面206。
请参阅图2、图3和图5,电化学装置100还包括第一绝缘层50。第一绝缘层50大致为片状,其覆盖第一表面201的至少一部分、第二表面202的至少一部分和第一端面204的至少一部分,并与第一表面201、第二表面202和第一端面204均相粘接。图5中,第一绝缘层50与用作第一表面201和第二表面202的两个极片的集流体的表面连接。第一绝缘层50在第一方向Z和第二方向Y上束缚电极组件20,降低热滥用和机械滥用中第一隔离膜23的第一部分23a靠近第一端面204的一端在第二方向Y上收缩导致第一极片21和第二极片22接触短路的风险,也可 以降低跌落中第一端面204所受到的应力,降低极片受损的风险。
请参阅图2和图3,定义电极组件20在第三方向X上的宽度为W1,定义第一绝缘层50在第三方向X上的宽度为W2,其中0.7W1≤W2≤W1。在W2<0.7W1的情况下,第一绝缘层50的宽度较小,第一绝缘层50与第一端面204之间的连接面积较小,即第一绝缘层50与第一隔离膜23之间的连接面积较小,因此在热箱及跌落过程中第一隔离膜23容易发生收缩导致内短路。在一些实施例中,W2≤0.95W1,有利用平衡制造过程中设置第一绝缘层50的公差,以及提高第一端面204的电解液浸润效果。
请参阅图2至图4,在一些实施例中,电化学装置100还包括第四绝缘层60和第三绝缘层70。第四绝缘层60大致为片状,其覆盖第一表面201的至少一部分、第二表面202的至少一部分和第一侧面205的至少一部分,并与第一表面201、第二表面202和第一侧面205均相连接。第四绝缘层60在第一方向Z和第三方向X上束缚电极组件20,降低第一隔离膜23的第一部分23a靠近第一侧面205的一端在第三方向X上收缩的风险。第三绝缘层70大致为片状,其覆盖第一表面201的至少一部分、第二表面202的至少一部分和第二侧面206的至少一部分,并与第一表面201、第二表面202和第二侧面206均相连接。第三绝缘层70在第一方向Z和第三方向X上束缚电极组件20,降低第一隔离膜23的第一部分23a靠近第二侧面206的一端在第三方向X上收缩的风险。
请参阅图2、图3和图5,在一些实施例中,电化学装置100还包括第二绝缘层80。第二绝缘层80大致为片状,其覆盖第一表面201的至少一部分、第二表面202的至少一部分和第二端面203的一部分,并与第一表面201、第二表面202和第二端面203均相连接。第二绝缘层80在第一方向Z和第二方向Y上束缚电极组件20,降低第一隔离膜23的第一部分23a靠近第二端面203的一端在第二方向Y上收缩的风险。本实施例中,电化学装置 100包括三个第二绝缘层80,其中一个第二绝缘层80设置于第一金属板30和第二金属板40之间,一个第二绝缘层80设置于第一金属板30和第一侧面205之间,一个第二绝缘层80设置于第二金属板40和第二侧面206之间,如此增加第二绝缘层80与第二端面203的连接面积,保持第二绝缘层80与第二端面203的粘接力,进一步降低第一隔离膜23的第一部分23a靠近第二端面203的一端收缩的风险。
在一些实施例中,第一绝缘层50、第四绝缘层60、第三绝缘层70和第二绝缘层80均具有粘性,并与电极组件20相粘接。第一绝缘层50、第四绝缘层60、第三绝缘层70和第二绝缘层80的材料均可以为单面胶或双面胶。
请参阅图6,第一隔离膜23具有层叠膜结构。具体地,第一隔离膜包括基材层231和间隔设置于基材层231的一表面的多个第一涂层232,第一涂层232粘结第一极片21。在另一实施例中,第一涂层232也可以粘结第二极片22。相邻的两个第一涂层232之间具有间隙G1。多个第一涂层232之间的间隙G1为电解液传输预留空间,在注液后,电解液能够经流间隙G1并充分地浸润极片。在这种情况下,即使设置第一绝缘层50以在第一方向Z和第二方向Y上束缚电极组件20,电解液依然能够通过间隙G1浸润极片。
在一实施例中,第一涂层232包括层叠设置的第一无机颗粒层232a和第一粘接层232b。第一无机颗粒层232a与基材层231相接,第一粘接层232b设置于第一无机颗粒层232a背离基材层231的表面,第一隔离膜23通过第一粘接层232b与相邻的极片粘接。第一粘接层232b能够粘接极片,提高第一隔离膜23与极片的界面粘结力,减少电化学装置100内部产气时的膨胀变形,即提高电化学装置100的抗变形能力,减小电极组件20变形和结构被破坏的风险,从而改善电化学装置100的循环性能。
请参阅图7,第一涂层232呈条状设置于基材层231的表面, 且多个第一涂层232相互平行设置。基材层231包括在第二方向Y上相对的两个侧边231a。第一涂层232与所述侧边231a的夹角为θ1。第一涂层232相对侧边231a倾斜设置,即0°<θ1<90°,因此,第一涂层232与极片之间的粘结力在电极组件在第二方向Y和第三方向X上的边缘上连续分布,提高电极组件抗变形的能力,改善循环性能。在一些实施例中,25°≤θ1≤65°,以保持第一涂层232与极片边缘的粘接力,遏制极片的边缘变形,从而提高循环性能。在θ1<25°的情况下,由于第一涂层232与第三方向X较为平齐,因此第一隔离膜23与极片在第二方向Y上的粘附性可能会降低,导致电极组件20在第三方向X上的边缘可能变形,影响循环寿命。在θ1>65°的情况下,由于第一涂层232与第二方向Y较为平齐,因此第一隔离膜23与极片在第三方向X上的粘附性可能会降低,导致电极组件20在第二方向Y上的边缘可能变形,影响循环寿命。
如图7所示,在一些实施例中,沿第一方向Z观察,第一涂层232的宽度为D1,相邻两个第一涂层232之间的距离为D2,其中,D1和D2满足:0.3D2≤D1≤0.5D2。当D1>0.5D2时,在极片面积一定的情况下,D2较小,使得可供电解液传输的空间减小,电解液浸润不良引发极片析锂问题,影响循环性能。当D1<0.3D2时,第一涂层232与极片之间的粘接面积减小,粘结力降低,抗变形能力也相应降低,影响循环性能。
如图6所示,在一些实施例中,第一隔离膜23还包括间隔设置于基材层231的一表面的多个第二涂层233,基材层231位于第一涂层232和第二涂层233之间。当第一涂层232粘结第一极片21时,第二涂层233粘结第二极片22。相邻的两个第二涂层233之间也具有间隙G2,作为供电解液传输的通道。因此,第二涂层233的设置进一步提高了电解液的浸润效果,进一步减少电解液浸润不良引发的极片析锂问题,从而提高循环性能。
第二涂层233包括层叠设置的第二无机颗粒层233a和第二 粘接层233b。第二无机颗粒层233a与基材层231相接,第二粘接层233b设置于第二无机颗粒层233a背离基材层231的表面。
在一些实施例中,基材层231包括以下任一种聚合物或两种以上的混合物形成的聚合物膜、多层聚合物膜、或无纺布:聚烯烃、聚偏氟乙烯、聚对苯二甲酸乙二醇酯、纤维素、聚酰亚胺、聚酰胺、氨纶和聚苯二甲酰苯二胺。此类聚合物具有较高的热稳定性,并且易于进行表面处理,从而易于在基材层231上涂覆第一涂层232和第二涂层233。另外,该类聚合物韧性较好,易于折弯。
第一无机颗粒层232a和第二无机颗粒层233a均包括无机颗粒材料,无机颗粒材料包括勃姆石、氢氧化铝或氢氧化镁颗粒中的至少一种。第一无机颗粒层232a和第二无机颗粒层233a还可以包括粘结剂,粘结剂将无机颗粒材料粘接在一起。粘结剂可以包括聚偏氟乙烯或偏二氟乙烯-六氟丙烯的共聚物。
第一粘接层232b和第二粘接层233b均包括粘结材料,粘结材料包括以下聚合物中的至少一种:偏二氟乙烯-六氟丙烯的共聚物、偏二氟乙烯-三氯乙烯的共聚物、聚甲基丙烯酸甲酯、聚丙烯酸、聚丙烯酸盐、聚丙烯腈、聚乙烯基吡咯烷酮、聚乙酸乙烯酯、乙烯-乙酸乙烯酯的共聚物、聚酰亚胺、聚氧化乙烯、乙酸纤维素、乙酸丁酸纤维素、乙酸丙酸纤维素、氰基乙基支链淀粉、氰基乙基聚乙烯醇、氰基乙基纤维素、氰基乙基蔗糖、支链淀粉、羧甲基纤维素钠、羧甲基纤维素锂、丙烯腈-苯乙烯-丁二烯的共聚物、聚乙烯醇、聚乙烯醚、聚四氟乙烯、聚六氟丙烯、苯乙烯-丁二烯的共聚物或聚偏二氟乙烯。这些聚合物能够产生较强的粘结作用,将第一隔离膜23和第一极片21或第二极片22粘结在一起。
请一并参阅图8,在一些实施例中,第二涂层233呈条状设置,多个第二涂层233相互平行设置。第二涂层233与所述侧边231a的夹角为θ2。第二涂层233相对侧边231a倾斜设置,即0° <θ2<90°。在一些实施例中,25°≤θ2≤65°,以保持第二涂层233与极片边缘的粘接力,进一步遏制极片的边缘变形,从而提高循环性能。在θ2<25°的情况下,由于第二涂层233与第三方向X较为平齐,因此第一隔离膜23与极片在第二方向Y上的粘附性可能会降低,导致电极组件20在第三方向X上的边缘可能变形,影响循环寿命。在θ2>65°的情况下,由于第二涂层233与第二方向Y较为平齐,因此第一隔离膜23与极片在第三方向X上的粘附性可能会降低,导致电极组件20在第二方向Y上的边缘可能变形,影响循环寿命。
如图8所示,第一涂层232和第二涂层233异面相交,第一涂层232和第二涂层233之间的夹角为θ3,0°<θ3<180°。如此多个第一涂层232之间的间隙G1和多个第二涂层233之间的间隙G2交错设置,进一步提高电解液浸润效果。如图9所示,在另一实施例中,第一涂层232和第二涂层233还可以平行设置,此时第一涂层232与侧边231a的夹角θ1与第二涂层233与侧边231a的夹角θ2相等。
请参阅图9,每一第一涂层232或每一第二涂层233可以为间断设置,如呈多个块状或多个岛状设置于基材层231的表面。此时,第一涂层232与侧边231a的夹角θ1即为多个块状部分或多个岛状部分的连线与侧边231a的夹角,第二涂层233与侧边231a的夹角θ2即为多个块状部分或多个岛状部分的连线与侧边231a的夹角。其中,间断设置的每一第一涂层232或间断设置的每一第二涂层233中也设有间隙G3,能够作为供电解液传输的通道,进一步提高电解液传输性能。
请参阅图10,在另一实施例中,第一隔离膜23的多个第一部分23a配置为一体,即第一隔离膜23一体设置。第一隔离膜23具有Z型折叠结构。具体地,在第一方向Z上,第一隔离膜23呈Z字形弯折形成Z型折叠结构。具有Z型折叠结构的第一隔离膜23仅包括两个端部,降低因第一隔离膜23收缩导致内短 路的风险,从而提高安全性能。
请参阅图11,在另一实施例中,第一隔离膜23还包括位于多个极片外并在第一方向Z上相对的第二部分23b和第三部分23c,其中,第二部分23b背离极片的表面作为电极组件20的第一表面201与第一绝缘层连接,第三部分23c背离极片的表面作为电极组件20的第二表面202与第一绝缘层连接。第一隔离膜23的多个第一部分23a、第二部分23b和第三部分23c配置为一体并形成卷绕结构,多个极片位于该卷绕结构中。具体地,第一隔离膜23以其一端为中心绕第二方向Y依次卷绕每n个极片形成卷绕结构,其中n为大于或等于1的整数。即,每相邻的两个第一部分23a之间设有n个极片。图11中示出了相邻的两个第一部分23a之间设有3个极片。在n大于或等于2的情况下,相邻的两个第一部分23a之间的多个极片之间也设置有第二隔离膜24。第二隔离膜24由绝缘材料制成,用于防止相邻的两个第一部分23a之间的多个极片直接接触而短路。第二隔离膜24的材料可以包括聚烯烃、聚偏氟乙烯、聚对苯二甲酸乙二醇酯、纤维素、聚酰亚胺、聚酰胺、氨纶或聚苯二甲酰苯二胺中的至少一种。
将一体设置的第一隔离膜23配置为卷绕结构,第一隔离膜23整体在第一方向Z和第三方向X上束缚多个极片,无需额外配置在第一方向Z上和第三方向X上束缚电极组件20的第二绝缘层和第三绝缘层。相较配置在第一方向Z和第三方向X上束缚电极组件20的第二绝缘层和第三绝缘层的情况,配置为卷绕结构的第一隔离膜23对极片在第三方向X上的边缘的束缚更弱,利于电解液流经极片在第三方向X上的边缘并充分地浸润极片。再者,第一隔离膜23包括位于多个极片外的第二部分23b和第三部分23c,第一绝缘层50与第一隔离膜23的第二部分23b和第三部分23c连接,第一隔离膜23的表面粗糙度大于极片的集流体的表面粗糙度,增大第一绝缘层50与电极组件20的粘结 力,降低第一绝缘层50脱落的风险。
请参阅图12,本申请一实施方式还提供一种用电设备1,用电设备1包括如上电化学装置100。本申请的用电设备1可以是,但不限于,笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备电子源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
以下通过具体实施例和对比例对本申请作详细说明。其中,以电化学装置为软包电芯为例并结合具体制备过程和测试方法对本申请进行说明,本领域技术人员应理解,本申请中描述的制备方法仅是实例,其他任何合适的制备方法均在本申请的范围内。
实施例1
将无机颗粒材料和粘结剂混合形成的浆料间隔涂布在基材层的表面形成间隔设置的多个第一无机颗粒层,然后将粘结材料涂布在多个第一无机颗粒层的表面形成多个第一粘接层以得到间隔设置的多个第一涂层,然后将无机颗粒材料和粘结剂混合形成的浆料间隔涂布在基材层的另一表面形成间隔设置的多个第二无机颗粒层,然后将粘结材料涂布在多个第二无机颗粒层的表面形成多个第二粘接层以得到间隔设置的多个第二涂层,得到第一隔离膜。其中,第一涂层的宽度D1和相邻两个第一涂层之间的距离D2的关系为D1=0.3D2,第一涂层与基材层的侧边的夹角θ1为45°
将第一隔离膜和多个极片进行卷叠得到电极组件,其中第一隔离膜具有卷绕结构,两个相邻的第一隔离膜的第一部分之间设有3个极片,第一隔离膜的第二部分和第三部分背离极片的表面作为电极组件的第一表面和第二表面。将第一绝缘层粘接于电极 组件的第一表面、第二表面和第二端面,其中第一绝缘层的宽度W2和电极组件的宽度W1的关系为:W2=0.8W1
将电极组件和电解液封装至铝塑膜内,得到电化学装置。
实施例2-13
与实施例1的不同之处在于,D1/D2的取值、W2/W1的取值、和夹角θ1的取值三者中至少一者不同。
对比例1
与实施例1的不同之处在于,浆料连续涂布在基材层的表面形成第一无机颗粒层和第二无机颗粒层,浆料连续涂布在第一无机颗粒层的表面和第二无机颗粒层的表面形成第一粘接层。即,使实施例1中间隔设置的多个第一涂层和多个第二涂层分别连接为一体。
对对比例1和实施例1-10、12-13的电化学装置进行循环测试,测试结果记录于表1中。其中,循环测试的步骤包括:采用在45摄氏度中,以1C恒定电流将电化学装置充电至4.43V,然后恒压充电至0.05C,接着静置5min,再采用0.7C放电至3.0V,采用市售电池性能测试机测得此时的放电容量为电化学装置首次放电容量,计为100%;按以上充放电步骤依次循环1000圈,循环后电化学装置放电容量与首次容量的比值乘以100%即为容量保持率;电化学装置按照充电流程充满,拆解观察负极极片界面情况以及析锂情况。
表1

比较对比例1和实施例1-10、12-13可知,在采用具有较宽宽度的第一绝缘层在第一方向上束缚电极组件时,当第一涂层和第二涂层连续涂覆于基材层的两个表面时,会导致严重电解液浸润不良,在极片的主体区(靠近极片的中心的区域)产生大量紫斑析锂,影响电化学装置的寿命;而当第一涂层和第二涂层间断涂覆于基材层的两个表面时,相邻第一涂层及相邻第二涂层之间的间隙为电解液传输预留空间,提高电解液浸润效果,提高电化学装置的寿命。因此,对比例1的循环容量保持率最低。
比较实施例1-3、9-10可知,当满足0.3D2≤D1≤0.5时,循环后负极极片界面良好,电化学装置具有较高的容量保持率;当D1过小时,第一隔离膜与极片的粘接面积太小导致电化学装置整体机械强度变低,在循环过程中易产生变形导致界面不良;当D1过大时,第一隔离膜上的电解液传输预留空间太小,导致浸润不良,进而引起界面不良。
比较实施例2、7、8、12-13可知,当满足25°≤θ1≤65°时,循环后负极极片界面良好,电化学装置具有较高的容量保持率;当θ1过小或过大时,极片的边缘易变形导致界面不良。
比较实施例2、4-6可知,当满足0.7W1≤W2时,循环后负极极片界面良好,电化学装置具有较高的容量保持率;且随着W2/W2增大,循环容量保持率呈现先提高后保持不变的趋势,W2≥0.85W1时电化学装置具有更高的容量保持率。
对对比例1和实施例2、14的电化学装置进行热箱测试,测试结果记录于表2中。其中,热箱测试的步骤包括:在25±5℃下,以0.2C恒定电流将电化学装置充电至4.43V,然后恒压充电至0.01C。将电化学装置以5±2℃/min的速率升温至140±2℃,而后保持60min。观察电化学装置是否有起火爆炸等失效现象,如没有,则通过热箱测试,反之则未通过。统计20个电化学装置的热箱测试通过率。测试结束后,对电化学装置进行拆解,观察是否出现隔膜收缩。
表2
比较对比例1和实施例2可知,在第一隔离膜的第二部分和第三部分的表面作为电极组件的第一表面和第二表面情况下,即在电极组件采用第一隔离膜收尾的情况下,将第一涂层和第二涂层间隔涂覆于基材层的两个表面,提高热箱测试通过率,且改善第一隔离膜的收缩。
对实施例1-6、9、11的电化学装置进行跌落测试,测试结果记录于表3中。跌落测试的步骤包括:在25±5℃下,以0.2C恒定电流将电化学装置充电至4.43V,然后恒压充电至0.01C。将 电化学装置固定在跌落测试夹具中,在1.8m高度下,按照跌落测试夹具的6个面依次跌落6次。每次跌落后观察电化学装置是否有破损,并测量电化学装置的开路电压,若电压小于3.0V即判定为电化学装置失效。若未出现破损,开路电压高于3.0V即判定为未失效,继续测试至失效,记录电化学装置失效时已进行的跌落次数。随后对电化学装置进行拆解分析,观察是否出现隔膜收缩。
表3
比较实施例1-3、9可知,当满足0.3D2≤D1≤0.5D2时,电化学装置的跌落次数多,抗跌落性能较好。当D1过小时,第一隔离膜与极片的粘接面积较小,第一隔离膜对电极组件整体的束缚作用有限,极片之间、电极组件和壳体之间的相互冲击作用增加,易导致壳体破损。因此,实施例9的电化学装置的抗跌落性能最差。
比较实施例2、4-6、11可知,当满足0.7W1≤W2时,电化学装置的跌落次数多,抗跌落性能较好。实施例11中,W2过小,在跌落过程中出现第一隔离膜收缩导致的失效,跌落次数最少,抗跌落性能最差。
以上所揭露的仅为本申请较佳实施方式而已,当然不能以此来限定本申请,因此依本申请所作的等同变化,仍属本申请所涵盖的范围。

Claims (17)

  1. 一种电化学装置,其特征在于,包括:
    壳体;
    电极组件,收容于所述壳体中,所述电极组件包括沿第一方向堆叠的多个极片和配置在所述多个极片之间的第一隔离膜,所述电极组件还包括在所述第一方向上相对的第一表面和第二表面以及连接于所述第一表面和所述第二表面之间的第一端面;
    第一绝缘层,与所述第一表面、所述第二表面和所述第一端面均相粘接;和
    电解液,收容于所述壳体中;
    其中,所述第一隔离膜包括基材层和间隔设置于所述基材层面向相邻的所述极片的表面的第一涂层。
  2. 如权利要求1所述的电化学装置,其特征在于,所述第一涂层呈条状,所述基材层包括在与所述第一方向垂直的第二方向上相对的两个侧边,所述多个第一涂层相对所述侧边倾斜设置。
  3. 如权利要求2所述的电化学装置,其特征在于,沿所述第一方向观察时,所述第一涂层与所述侧边的夹角为θ1,25°≤θ1≤65°。
  4. 如权利要求2所述的电化学装置,其特征在于,沿所述第一方向观察时,所述第一涂层的宽度为D1,相邻的两个第一涂层之间的间距为D2,0.3D2≤D1≤0.5D2
  5. 如权利要求2所述的电化学装置,其特征在于,所述第一隔离膜还包括多个第二涂层,所述多个第二涂层间隔设置于所述基材层背离所述多个第一涂层的表面。
  6. 如权利要求5所述的电化学装置,其特征在于,所述第一涂层和所述第二涂层异面相交。
  7. 如权利要求1所述的电化学装置,其特征在于,所述第一隔离膜包括位于所述多个极片中的多个第一部分以及位于所述多个极片外并在所述第一方向上相对的第二部分和第三部分,每 个所述第一部分配置于相邻的两个极片之间,所述多个第一部分、所述第二部分和所述第三部分配置为一体并形成卷绕结构。
  8. 如权利要求1所述的电化学装置,其特征在于,在与所述第一方向垂直的第三方向上,所述电极组件的宽度为W1,所述第一绝缘层的宽度为W2,0.7W1≤W2≤W1
  9. 如权利要求8所述的电化学装置,其特征在于,0.7W1≤W2≤0.95W1
  10. 如权利要求9所述的电化学装置,其特征在于,0.85W1≤W2≤0.95W1
  11. 如权利要求1所述的电化学装置,其特征在于,所述第一涂层包括第一无机颗粒层和第一粘接层,所述第一无机颗粒层与所述基材层相接,所述粘接层设置于所述无机颗粒层背离所述基材层的表面并与相邻的所述极片粘接。
  12. 如权利要求1所述的电化学装置,其特征在于,所述第一涂层包括无机颗粒和粘结剂。
  13. 如权利要求1所述的电化学装置,其特征在于,所述电化学装置还包括第二绝缘层,所述电极组件还包括连接于所述第一表面和所述第二表面之间的第二端面,定义所述电极组件的长度方向为第二方向,所述第一表面和所述第二表面在所述第二方向上相对,所述第二绝缘层与所述第一表面、所述第二表面和所述第二端面均相连接。
  14. 如权利要求13所述的电化学装置,其特征在于,所述第一绝缘层为单面胶或双面胶,和/或所述第二绝缘层为单面胶或双面胶。
  15. 如权利要求1所述的电化学装置,其特征在于,所述电化学装置还包括第一金属板和第二金属板,所述第一金属板和所述第二金属板均与所述电极组件连接;在与所述第一方向垂直的第三方向上,所述电极组件还包括与所述第一端面相对的第二端面,所述第一金属板和所述第二金属板从所述第二端面伸出所述 电极组件。
  16. 如权利要求1所述的电化学装置,其特征在于,所述壳体为包装袋。
  17. 一种用电设备,其特征在于,包括如权利要求1至16中任一项所述的电化学装置。
PCT/CN2023/099742 2023-06-12 2023-06-12 电化学装置及包含其的用电设备 Ceased WO2024254743A1 (zh)

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