WO2022214095A1 - Battery separator for energy storage device, preparation process thereof, preparation system therefor, and energy storage device - Google Patents

Battery separator for energy storage device, preparation process thereof, preparation system therefor, and energy storage device Download PDF

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Publication number
WO2022214095A1
WO2022214095A1 PCT/CN2022/085955 CN2022085955W WO2022214095A1 WO 2022214095 A1 WO2022214095 A1 WO 2022214095A1 CN 2022085955 W CN2022085955 W CN 2022085955W WO 2022214095 A1 WO2022214095 A1 WO 2022214095A1
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Prior art keywords
layer
film
energy storage
storage device
positive electrode
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PCT/CN2022/085955
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French (fr)
Chinese (zh)
Inventor
庄志
鲍晋珍
刘倩倩
蔡裕宏
程跃
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上海恩捷新材料科技有限公司
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Priority claimed from CN202111068351.2A external-priority patent/CN113809470A/en
Application filed by 上海恩捷新材料科技有限公司 filed Critical 上海恩捷新材料科技有限公司
Publication of WO2022214095A1 publication Critical patent/WO2022214095A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity

Definitions

  • the invention relates to the field of energy storage devices, in particular to a battery film for energy storage devices and a preparation process thereof, a system and an energy storage device.
  • the basic structure includes a positive current collector layer, a positive active layer, a porous Diaphragm layer, negative electrode active layer, and negative electrode current collector layer, in the existing preparation process, all are first to prepare the finished porous diaphragm layer and the current collector layer laminated with the active layer, and then press the two according to the structural sequence to obtain lithium ions Therefore, there are technical bottlenecks such as low production efficiency and the inability to make further breakthroughs in ultra-thin lithium-ion batteries under the same energy density.
  • the invention provides a battery film for an energy storage device, which comprises a positive electrode layer and an intermediate film in sequence.
  • the present invention also provides an energy storage device, which sequentially includes a positive electrode current collector, the above-mentioned battery film, and a negative electrode current collector.
  • the invention also provides a process for preparing a battery film for an energy storage device, which sequentially includes: forming the intermediate film, coating the intermediate film on-line, and forming the battery film.
  • the present invention also provides a preparation system of a battery film for an energy storage device, comprising: a multi-section oven is arranged in the traveling route of the intermediate film for shaping, and a coating layer for the intermediate film coating slurry is arranged at the interval between the adjacent ovens. cloth device.
  • the beneficial effects of the present invention are: to provide a battery film, which can change the production mode of traditional energy storage devices, and can be directly combined with positive electrode current collectors and negative electrode current collectors to form energy storage devices. While improving the production efficiency of energy devices and greatly reducing production costs, based on the innovation of battery membrane structure, online coating technology and dry battery technology, high energy density and high safety energy storage devices are obtained.
  • Fig. 1 is the structural schematic diagram of the battery film of the present invention
  • the present invention provides a battery film, which at least includes a positive electrode layer and an intermediate film in order to control the thickness of the battery film, and further, a battery
  • the film can also include a positive electrode layer, an intermediate film, and a negative electrode layer in sequence, and the area of the battery film close to the intermediate film is the inner side, and vice versa; the battery film prepared by the present invention can be directly pressed and laminated with the positive electrode current collector layer and the negative electrode current collector layer.
  • the positive electrode layer can be single-layer or multi-layer, which is a functional layer that is dry-pressed on one side of the intermediate film as a film layer or coated on one side of the intermediate film as a coating layer.
  • the positive electrode layer may be a positive electrode bonding layer.
  • the positive active layer is also a uniform monolayer formed by mixing the positive active material, the conductive agent and the binder.
  • the optimal proportion between the positive active material, the conductive agent and the binder is calculated according to the weight ratio. It is: 90:5:5 to 99:0.5:0.5.
  • the positive electrode layer can also be a multi-layer comprising a positive electrode active layer and a positive electrode bonding layer from the inside to the outside near the intermediate film, or further, as shown in Figure 1, the positive electrode layer can also be adjacent to the intermediate film 1 from the inside to the outside. It includes a multi-layered positive electrode active layer 2, a positive electrode conductive layer 3, and a positive electrode bonding layer 4; it can also include a positive electrode bonding layer, a positive electrode active layer, and a positive electrode conductive layer from the inside to the outside near the intermediate film.
  • the above-mentioned conductive agent or positive electrode conductive layer may be a carbon material, preferably any one or a combination of conductive carbon black, graphene, graphite microspheres, and the like.
  • the above-mentioned binder or positive electrode binder may include at least any one or a combination of PVDF, SBR, acrylate, PAA, and polyurethane.
  • the positive electrode layer When the positive electrode layer has a single-layer or multi-layer structure, as mentioned above, it can be dry-pressed on the intermediate film in the order of the laminated structure. Dry spraying, dry electrostatic spraying, etc. are arranged on the interlayer;
  • the functional layers close to the intermediate film can also be sequentially coated and dried in the form of slurry.
  • the coating methods can be listed as extrusion coating and transfer coating. , (micro) gravure coating, spray coating, dip coating and wire rod coating, ion sputtering, PVD, CVD, screen printing, etc.
  • extrusion coating and transfer coating a coating method for sequentially extrude and coat the positive electrode adhesive layer slurry.
  • in-line coating is used to sequentially extrude and coat the positive electrode adhesive layer slurry, The positive electrode conductive layer slurry and the positive electrode active layer slurry are sequentially dried, and finally a film is formed.
  • the intermediate film can be single-layer or multi-layer, and is a functional layer used to support or separate the positive and negative electrodes of the energy storage device. A sort of.
  • the intermediate film when the intermediate film is a porous film, it can be a single-layer or multi-layer porous base film, at least polyolefin, PET, etc. can be listed, and at least one side of the porous base film can be coated with an organic or inorganic coating ,
  • organic and inorganic coatings the materials that can be listed are at least inorganic oxides, inorganic salts, polyimide, PVDF, polyester, etc.; among them, inorganic oxides can be listed as alumina, boehmite, Mg/ Metal oxides such as Al/Be/Si; when the intermediate film is a coating film, the coating method of the coating film can be gravure coating, spray coating, dip coating, wire bar coating, blade coating, spray coating and roll coating, Any one of screen printing, online coating, etc.
  • the online coating here means that compared with the traditional coating film, the porous base film preparation process and the coating process are divided into two independent procedures or production lines. After coating, the coating and the porous base film are dried and shaped at the same time, and the two can be mutually regulated, which not only saves the steps of heat setting and winding of the porous base film, but also obtains better thickness, porosity and consistency of the intermediate film. The bonding force with the positive electrode layer is stronger.
  • the types that can be listed are at least polymer solid electrolyte, oxide solid electrolyte, oxide crystalline solid electrolyte, LiPON type electrolyte, sulfide crystalline solid electrolyte, sulfide glass and glass ceramic solid Electrolyte, the materials that can be listed are at least polyurethane, PEO, PAN, DOL, polycarbonate, PVDF, lithium nitride, fast ion conductor material, wherein, fast ion conductor material can be sodium ion, Mg ion, Zn ion, K ion , Al ions, etc. one or more, such as lithium titanium aluminum phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum thallium oxygen,.
  • the intermediate film When the intermediate film is a porous film, at least it can be prepared by dry stretching, wet phase separation, electrospinning, papermaking and other processes. In particular, the intermediate film is at least one side of the porous base film.
  • the intermediate membrane When coated with an organic or inorganic coating, the intermediate membrane can be prepared by an online coating process; when the intermediate membrane is a solid electrolyte membrane, it can be prepared at least by processes such as papermaking, sintering, casting and casting, and electrospinning. .
  • the negative electrode layer can be a single layer or a multi-layer, which is a functional layer that is dry-pressed on one side of the intermediate film as a film layer or coated on one side of the intermediate film as a coating.
  • the negative electrode layer can be a negative electrode current collector layer. Compared with the prior art, without the negative electrode active material, the energy density of the energy storage device can be improved, and the purpose of reducing the thickness of the energy storage device and reducing the cost is achieved.
  • the negative electrode layer can be a uniform monolayer formed by mixing the negative electrode active material, the conductive agent and the binder; after the negative electrode active material is mixed with the conductive agent and the binder, each component is based on the weight ratio, and the optimal ratio is The interval is: 90:5:5 ⁇ 99:0.5:0.5, among which, the negative electrode active material can at least include carbon materials and silicon-based materials, and the carbon materials can at least include natural graphite, artificial graphite, hard carbon, and mesophase carbon microstructure. Balls, Graphene.
  • the negative electrode layer can also be a multi-layer that includes a negative electrode active layer and a negative electrode bonding layer in turn near the intermediate film, or further, the negative electrode layer can also be a multi-layer that includes a negative electrode active layer, a negative electrode conductive layer, and a negative electrode bonding layer in turn adjacent to the intermediate film.
  • the layer can also include a negative electrode bonding layer, a negative electrode active layer, and a negative electrode conductive layer in sequence from the inside to the outside near the intermediate film.
  • the above-mentioned binder or negative electrode binder may include at least any one or a combination of PVDF, PVDF-HFP, SBR, acrylate, PAA, and polyurethane.
  • the specific structure of the battery film can be any combination or combination of the above-mentioned layer structure schemes.
  • the negative electrode layer When the negative electrode layer has a single-layer or multi-layer structure, as mentioned above, it can be dry-pressed on the intermediate film in the order of the laminated structure. Dry spraying, dry electrostatic spraying, etc. are arranged on the interlayer;
  • the functional layers close to the intermediate film can also be sequentially coated and dried in the form of slurry.
  • the coating methods can be listed as extrusion coating and transfer coating. , (micro) gravure coating, spray coating, dip coating and wire rod coating, ion sputtering, PVD, CVD, evaporation, magnetron sputtering, vacuum plating, etc.
  • the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, The negative electrode conductive layer slurry and the negative electrode active layer slurry are sequentially dried, and finally a film is formed.
  • the method for producing the above-mentioned high-energy-density battery film is not particularly limited as long as a battery film having the above-mentioned structure can be obtained.
  • the present invention provides a preparation process, which sequentially includes: forming the intermediate film, on-line coating of the intermediate film, and forming the battery film.
  • the above setting may be any one of normal temperature setting, low temperature setting, radiation setting, pressure setting, chemical or electrochemical reaction curing setting.
  • the preparation process sequentially includes: heat setting of the intermediate film, on-line coating of the intermediate film, and heat setting of the battery film.
  • the thermal setting of the intermediate film and the drying of the coating layer by layer are synchronized. It can effectively improve production efficiency and reduce production costs.
  • this process can shorten the production time, and the obtained battery film
  • the consistency is better, the bonding force between the coating and the interlayer is stronger, the interface impedance level is excellent, the flexibility is better, and the shape and size are more flexible.
  • the above-mentioned coating process corresponds to a coating system for a battery separator, including: a plurality of film setting devices are arranged in the traveling route of the intermediate film setting, and a spacer for the intermediate film coating slurry is arranged at the interval position of the adjacent film setting devices. coating device.
  • the membrane setting device and coating device are not particularly limited, and the number or type can be selected according to the preparation process and the stacking structure of the positive electrode layer or the negative electrode layer.
  • a multi-section oven is provided in the traveling route of the heat-setting of the interlayer, and a coating device for coating slurry of the interlayer is provided at the interval between adjacent ovens.
  • each subgroup includes a coating device, a preliminary heat setting oven located upstream of the coating device for preliminary drying of the interlayer film, The coating and heat-setting oven downstream of the cloth device is used for drying the battery film.
  • the number of ovens can be reduced or added according to actual needs.
  • the energy storage devices of the present invention include but are not limited to the fields of lithium ion batteries, sodium ion batteries, magnesium ion batteries, zinc ion batteries, solid-state batteries, semi-solid-state batteries, lithium-sulfur batteries, and flow batteries, and specifically, include positive electrode current collectors in sequence.
  • the battery film of any one of the above, the negative electrode current collector wherein, the material of the positive electrode current collector at least has a conductive material, and the conductive material is preferably Cu, AL, Ni; the material of the negative electrode current collector has at least a conductive material or a negative electrode metal material, and the negative electrode metal
  • the material is preferably lithium metal and sodium metal.
  • the battery film of the present invention when used in an energy storage device, especially in the field of solid-state batteries or semi-solid state, compared with the prior art, the energy storage device prepared by the present invention has a lower interface impedance than the prior art. The necessary options can still achieve good rate performance, low temperature charge and discharge, and long cycle life.
  • the energy storage device sequentially includes a positive electrode sheet (including a positive electrode current collector and a positive electrode active material), a battery film, and a negative electrode current collector.
  • the positive electrode current collector, the negative electrode current collector and the battery film are composited, at least ion sputtering, PVD, CVD, off-line composite, lamination and other methods can be used.
  • the positive and negative current collectors and the positive and negative films can also be combined with the dry electrode technology, using dry spraying or dry powder electrostatic spraying technology to obtain the positive and negative electrode pieces and then compound with the intermediate film to obtain the corresponding energy storage device.
  • a polyethylene porous diaphragm with a thickness of 9um is used, and a layer of lithium iron phosphate positive electrode layer with a thickness of 10um is formed on one side of the porous diaphragm by vacuum plating to form a battery film.
  • the compounding method is lamination compounding, wherein the anode layer side is compounded with aluminum foil, and the negative electrode layer side is compounded with copper foil.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a polyethylene porous membrane with a thickness of 9um is used.
  • One side of the porous membrane is coated with a positive electrode layer with a thickness of 80um to form a battery film.
  • the positive electrode layer is composed of NCM, PVDF and conductive carbon in a ratio of 96:2:2.
  • copper foil and aluminum foil are respectively arranged on both sides of the battery film to form an electrochemical device.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a polypropylene porous membrane with a thickness of 12um is used.
  • One side of the porous membrane is coated with a PVDF layer with a thickness of 2um and a positive electrode layer with a thickness of 80um to form a battery membrane.
  • the aluminum foil forms an electrochemical device.
  • the positive electrode current collector and the positive electrode layer are composited through the PVDF layer coated on the positive electrode layer.
  • the composite method of the negative electrode current collector is lamination composite, wherein the positive electrode layer side is composited with aluminum foil, and the negative electrode layer side is composited with copper foil.
  • a polypropylene porous membrane with a thickness of 12um is used.
  • One side of the porous membrane is vacuum-plated with an NCM positive electrode layer with a thickness of 10um, and then a PVDF layer is applied to form a battery film.
  • the foil and the aluminum foil form an electrochemical device.
  • the positive electrode current collector and the positive electrode layer are composited by the PVDF layer coated on the positive electrode layer.
  • the composite method of the negative electrode current collector is lamination composite, wherein the positive electrode layer side is composited with aluminum foil, and the negative electrode layer side is composited with copper foil.
  • a polyethylene porous membrane with a thickness of 9um is used.
  • One side of the porous membrane is vacuum-plated with an NCM positive electrode layer with a thickness of 10um.
  • a conductive carbon layer and a PVDF layer are sequentially coated on the positive electrode side to form a battery film. Then the battery The film composites the positive electrode current collector and the negative electrode current collector, wherein the positive electrode layer side is composited with aluminum foil, and the negative electrode layer side is composited with copper foil.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a polyethylene porous diaphragm with a thickness of 9um is used.
  • One side of the porous diaphragm is sequentially provided with a layer of PMMA coating and a NCA positive electrode layer with a thickness of 10um by in-line coating.
  • the conductive carbon layer and PVDF layer are coated to form a battery film, and then the positive electrode current collector and the negative electrode current collector are combined, wherein the positive electrode layer side is combined with aluminum foil, and the negative electrode layer side is combined with copper foil.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a polyethylene porous diaphragm with a thickness of 9um is used, and one side of the porous diaphragm is sequentially coated with an alumina coating, an LCO layer, a conductive carbon layer and a PVDF layer by successive online coating to form a battery film, and then the composite cathode current collector and A negative electrode current collector, wherein the positive electrode layer side is compounded with aluminum foil, and the negative electrode layer side is compounded with copper foil.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a polyethylene porous membrane with a thickness of 9um is used.
  • One side of the porous membrane is coated with alumina coating, PVDF layer and NCM layer by successive online coating.
  • the other side of the porous membrane is coated by online coating.
  • the negative electrode slurry is composed of Si:SBR:conductive carbon 90:5:5 to form a battery film, and then composite the positive electrode current collector and the negative electrode current collector, wherein the positive electrode layer side is composited with aluminum foil, and the negative electrode layer side is composited with copper foil.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a LLZTO layer with a thickness of 20 um is used, and an NCM with a thickness of 10 um is set on one side of the LLZTO by vacuum plating to form a battery film, and then the positive electrode current collector and the negative electrode current collector are compounded, wherein the positive electrode layer side is compounded with aluminum foil, and the negative electrode layer side is compounded Li metal.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • the LGPS layer with a thickness of 20um is used, and the NCM with a thickness of 10um is set on one side of the LGPS by vacuum plating, and then PVDF is coated on the other side of the NCM to form a battery film.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a PEO layer with a thickness of 20 um is used, and a layer of lithium iron phosphate, a conductive carbon layer and a PVDF layer with a thickness of 10 um are successively coated on one side of the PEO to form a battery film.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a polyethylene porous diaphragm with a thickness of 9um is used, and one side of the porous diaphragm is sequentially coated with alumina coating, multi-element Fe-based transition metal Na oxide layer, conductive graphene layer and PVDF layer by successive online coating.
  • the other side of the battery is coated with hard carbon, etc., conductive carbon layer and SBR layer in turn by in-line coating to form a battery film, and then both sides are compounded with aluminum foil current collectors.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a PEO film with a thickness of 20um is used.
  • One side of the PEO film is coated with a multi-element Fe-based transition metal Na oxide layer, a conductive carbon layer and a PVDF layer by successive online coating, and hard carbon is coated on the other side of the PEO film.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a polyethylene porous diaphragm with a thickness of 9um is used, and one side of the porous diaphragm is sequentially coated with alumina coating, multi-component Mn-based transition metal Na oxide layer, conductive graphene layer and PVDF layer by successive online coating. The other side is coated with a hard carbon layer to form a battery film, and then both sides are compounded with aluminum foil current collectors.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • a PEO film with a thickness of 20um was used, and one side of the PEO film was sequentially coated with a multi-element Fe-based transition metal Na oxide layer, a conductive graphene layer and a PVDF layer by successive online coating to form a battery film, and then both sides were composited and collected. Fluid, the positive side is compounded with Al current collector, and the negative side is compounded with Na metal current collector.
  • the above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
  • the positive electrode layer is composed of NCM, PVDF, and conductive carbon in a weight ratio of 90:5:5.
  • the positive electrode layer is composed of NCM, PVDF, and conductive carbon in a weight ratio of 99:0.5:0.5.
  • the negative electrode slurry is composed of Si:SBR:conductive carbon in a mass ratio of 99:0.5:0.5.
  • the negative electrode slurry is composed of Si:SBR:conductive carbon in a mass ratio of 95:2.5:2.5.
  • Impedance Connect the positive and negative electrodes of the battery membrane to the positive and negative electrodes of the electrochemical workstation, select the electrochemical impedance test item, set the disturbance voltage to 10mV, and the frequency range to 0.01Hz to 1,000,000Hz, and record the impedance value.
  • Peeling force between the intermediate film and the positive electrode layer 3M tape was used to stick on both sides of the intermediate layer and the positive electrode layer, respectively, and the sample was cut into a 15mm width, and two pieces of 3M tape were stretched in the direction of 180° with a universal tensile testing machine, respectively. The tensile speed was 50 m/min and the maximum peel force was recorded.
  • the energy density of the battery film charge and discharge with 0.5C current, record the discharge capacity C of the battery film and the voltage platform V, weigh the battery film and record it as M, the energy density calculation formula is C*V/M, and convert the unit. into Wh/kg.
  • Bendability of the battery film Hold the head and tail ends of the battery film with both hands and gently fold them in half. If the bending angle exceeds 45°C, it can be restored to its original state, which is recorded as bendable, otherwise it is recorded as not bendable.
  • the battery films and energy storage devices prepared in Examples 1 to 19 were subjected to the above performance tests under the same test environment, and the performance data were recorded in Table 1 below.
  • the battery film provided by the present invention can be directly pressed and compounded with the positive electrode current collector and the negative electrode current collector to obtain an energy storage device, and the internal resistance and energy density of the energy storage device maintain the leading level of the current industry technology , which can promote the improvement and development of the current energy storage device production process; and further simplify the production process and steps of the battery film through the on-line coating production method, and the obtained battery film has better consistency and the bonding force between the coating and the intermediate film. Stronger, the interface impedance maintains an excellent level, and the flexibility is better.

Abstract

The present invention relates to the field of energy storage devices, and specifically to a battery separator for an energy storage device, a preparation process thereof, a preparation system therefor, and an energy storage device. The battery separator for an energy storage device comprises a positive electrode layer and an intermediate separator in sequence. The battery separator effectively improves the production efficiency of the energy storage device, and obtains a high energy density and high safety energy storage device on the basis of the innovation of the structure of the battery separator and the in-line coating technology while greatly reducing the production cost.

Description

一种储能器件用的电池膜及其制备工艺、系统与储能器件A kind of battery film for energy storage device and its preparation process, system and energy storage device 技术领域technical field
本发明涉及储能器件领域，具体是一种储能器件用的电池膜及其制备工艺、系统与储能器件。The invention relates to the field of energy storage devices, in particular to a battery film for energy storage devices and a preparation process thereof, a system and an energy storage device.
背景技术Background technique
目前，储能器件存在例如锂离子电池、钠离子电池、固态电池、半固态电池、锂硫电池等方向，以锂离子电池为例，其基本结构依次包括正极集流体层、正极活性层、多孔隔膜层、负极活性层、负极集流体层，在现有的制备工艺上，均为先制得成品多孔隔膜层以及层叠有活性层的集流体层，再将二者按照结构顺序压制成型得到锂离子电池，因而存在生产效率低下、同等能量密度下超薄锂离子电池无法进一步突破等技术瓶颈。At present, energy storage devices exist such as lithium-ion batteries, sodium-ion batteries, solid-state batteries, semi-solid-state batteries, and lithium-sulfur batteries. Taking lithium-ion batteries as an example, the basic structure includes a positive current collector layer, a positive active layer, a porous Diaphragm layer, negative electrode active layer, and negative electrode current collector layer, in the existing preparation process, all are first to prepare the finished porous diaphragm layer and the current collector layer laminated with the active layer, and then press the two according to the structural sequence to obtain lithium ions Therefore, there are technical bottlenecks such as low production efficiency and the inability to make further breakthroughs in ultra-thin lithium-ion batteries under the same energy density.
发明内容SUMMARY OF THE INVENTION
本发明提供一种储能器件用电池膜，依次包括正极层、中间膜。The invention provides a battery film for an energy storage device, which comprises a positive electrode layer and an intermediate film in sequence.
本发明还提供一种储能器件，依次包括正极集流体、上述的电池膜、负极集流体。The present invention also provides an energy storage device, which sequentially includes a positive electrode current collector, the above-mentioned battery film, and a negative electrode current collector.
本发明还提供一种储能器件用电池膜的制备工艺，依次包括：中间膜定型、中间膜在线涂布、电池膜定型。The invention also provides a process for preparing a battery film for an energy storage device, which sequentially includes: forming the intermediate film, coating the intermediate film on-line, and forming the battery film.
本发明还提供一种储能器件用电池膜的制备系统，包括：在中间膜定型的行进路线中设置有多节的烘箱，相邻烘箱的间隔位置设置有用于中间膜涂覆浆料的涂布装置。The present invention also provides a preparation system of a battery film for an energy storage device, comprising: a multi-section oven is arranged in the traveling route of the intermediate film for shaping, and a coating layer for the intermediate film coating slurry is arranged at the interval between the adjacent ovens. cloth device.
本发明的有益效果在于：提供一种电池膜，能够改变传统储能器件生产模式，可直接与正极集流体、负极集流体组合构成储能器件，通过一体化的 电池膜生产，在有效提高储能器件生产效率，大幅度降低生产成本的同时，基于电池膜结构的创新以及在线涂布技术、干电池技术，得到高能量密度高安全储能器件。The beneficial effects of the present invention are: to provide a battery film, which can change the production mode of traditional energy storage devices, and can be directly combined with positive electrode current collectors and negative electrode current collectors to form energy storage devices. While improving the production efficiency of energy devices and greatly reducing production costs, based on the innovation of battery membrane structure, online coating technology and dry battery technology, high energy density and high safety energy storage devices are obtained.
附图说明Description of drawings
图1为本发明电池膜的结构示意图；Fig. 1 is the structural schematic diagram of the battery film of the present invention;
附图标记：Reference number:
1-中间膜；2-正极活性层、3-正极导电层、4-正极粘结层1-Interlayer; 2-Positive active layer, 3-Positive conductive layer, 4-Positive bonding layer
具体实施方式Detailed ways
在描述之前，应当理解，不应将在说明书和所附权利要求书中使用的术语解释为限于一般的词典含义，而应当根据允许本发明人为了最好的解释而合适地限定术语的原则，基于对应于本发明的技术方面的含义和概念进行解释。因此，在此提出的描述仅是为了说明目的而优选的例子，不是为了限制本发明的范围，因此，应当理解，可以在不背离本发明的精神和范围的情况下作出其它的等价物和修改。Before describing, it is to be understood that terms used in the specification and appended claims should not be construed to be limited to their ordinary dictionary meanings, but should be in accordance with principles that allow the inventor to define terms as appropriate for the best interpretation, The explanation is made based on meanings and concepts corresponding to the technical aspects of the present invention. Accordingly, the descriptions set forth herein are for illustrative purposes only of preferred examples and are not intended to limit the scope of the invention, it being understood, therefore, that other equivalents and modifications may be made without departing from the spirit and scope of the invention.
1. 电池膜 1. Battery film
基于目前储能器件生产效率低下，同等能量密度下储能器件厚度无法突破的技术问题，本发明提供一种电池膜，为控制电池膜厚度，其至少包括正极层、中间膜，进一步的，电池膜还可以依次包括正极层、中间膜、负极层，电池膜靠近中间膜的区域为内侧，反之为外侧；本发明所制得的电池膜可直接与正极集流层、负极集流层压制层叠制成厚度在100nm～100um之间且高能量密度、可弯折的储能器件，并改变目前储能器件的生产流程与模式，有效提高储能器件的生产效率，以下将逐一进行说明。Based on the technical problems of low production efficiency of the current energy storage device and the inability to break through the thickness of the energy storage device under the same energy density, the present invention provides a battery film, which at least includes a positive electrode layer and an intermediate film in order to control the thickness of the battery film, and further, a battery The film can also include a positive electrode layer, an intermediate film, and a negative electrode layer in sequence, and the area of the battery film close to the intermediate film is the inner side, and vice versa; the battery film prepared by the present invention can be directly pressed and laminated with the positive electrode current collector layer and the negative electrode current collector layer. To make energy storage devices with a thickness between 100nm and 100um, high energy density and bendable, and change the current production process and mode of energy storage devices, effectively improve the production efficiency of energy storage devices, the following will be explained one by one.
1.1 正极层 1.1 Positive electrode layer
1.1.1 结构与材料 1.1.1 Structure and Materials
正极层可以单层或多层，其是做为膜层干压在中间膜的一侧或做为涂层涂覆在中间膜一侧的功能层。The positive electrode layer can be single-layer or multi-layer, which is a functional layer that is dry-pressed on one side of the intermediate film as a film layer or coated on one side of the intermediate film as a coating layer.
正极层可以为正极活性层单层，本发明对正极活性层的材料可以为储能器件领域习知的活性材料的一种或多种，可列举的材料至少有磷酸钒钠、普鲁士蓝、普鲁士白、聚阴离子型正极材料如NaMnPO4、NaFePO4、二维层状过渡金属化合物如NaxMO4(M＝Co、Mn、V、Fe)，过渡金属磷酸盐，空心或核壳纳米材料，空心硒化钴纳米立方、Fe-N共参杂核壳钒酸钠纳米球、多孔碳空心氧化锡纳米球等，硫单质或硫化物，锂镍氧化物，锂钴氧化物，锂钛氧化物，镍钴多元氧化物，锂锰氧化物，锂铁磷氧化物，含Mg离子、Zn离子、K离子、Al离子等的电化学活性材料，本发明在形成正极活性层时，无溶剂挥发，清洁环保。The positive electrode layer can be a single layer of the positive electrode active layer, and the material of the positive electrode active layer of the present invention can be one or more kinds of active materials known in the field of energy storage devices, and the listed materials are at least sodium vanadium phosphate, Prussian blue, Prussian White, polyanionic cathode materials such as NaMnPO4, NaFePO4, two-dimensional layered transition metal compounds such as NaxMO4 (M=Co, Mn, V, Fe), transition metal phosphates, hollow or core-shell nanomaterials, hollow cobalt selenide nanomaterials Cubic, Fe-N co-doped core-shell sodium vanadate nanospheres, porous carbon hollow tin oxide nanospheres, etc., sulfur element or sulfide, lithium nickel oxide, lithium cobalt oxide, lithium titanium oxide, nickel cobalt multi-component oxide compound, lithium manganese oxide, lithium iron phosphorus oxide, and electrochemically active materials containing Mg ion, Zn ion, K ion, Al ion, etc., when the positive electrode active layer is formed, the present invention has no solvent volatilization, and is clean and environmentally friendly.
正极层可以为正极粘结层。The positive electrode layer may be a positive electrode bonding layer.
除此之外，正极活性层还为正极活性材料和导电剂、粘结剂混合后形成的均匀单层，正极活性材料和导电剂、粘结剂之间按重量比计，最优占比区间为：90:5：5～99:0.5:0.5。In addition, the positive active layer is also a uniform monolayer formed by mixing the positive active material, the conductive agent and the binder. The optimal proportion between the positive active material, the conductive agent and the binder is calculated according to the weight ratio. It is: 90:5:5 to 99:0.5:0.5.
正极层亦可以为靠近中间膜由内至外依次包括正极活性层、正极粘结层的多层，或者更进一步，如图1所示，正极层亦可以为靠近中间膜1由内至外依次包括正极活性层2、正极导电层3、正极粘结层4的多层；也可以为靠近中间膜由内至外依次包括正极粘结层、正极活性层，正极导电层。The positive electrode layer can also be a multi-layer comprising a positive electrode active layer and a positive electrode bonding layer from the inside to the outside near the intermediate film, or further, as shown in Figure 1, the positive electrode layer can also be adjacent to the intermediate film 1 from the inside to the outside. It includes a multi-layered positive electrode active layer 2, a positive electrode conductive layer 3, and a positive electrode bonding layer 4; it can also include a positive electrode bonding layer, a positive electrode active layer, and a positive electrode conductive layer from the inside to the outside near the intermediate film.
上述导电剂或正极导电层可以为碳材料，优选导电炭黑、石墨烯、石墨微球等中的任意一种或组合。The above-mentioned conductive agent or positive electrode conductive layer may be a carbon material, preferably any one or a combination of conductive carbon black, graphene, graphite microspheres, and the like.
上述粘结剂或正极粘结剂可列举的至少有PVDF、SBR、丙烯酸酯、PAA、聚氨酯中的任意一种或组合。The above-mentioned binder or positive electrode binder may include at least any one or a combination of PVDF, SBR, acrylate, PAA, and polyurethane.
1.1.2 制备工艺 1.1.2 Preparation process
当正极层为单层或多层结构时，如前述，可按照层叠结构顺序干压至中间膜上，其中干压可以是在一定温度下施加压力，温度范围为0～90℃，也可以采用干喷法、干法静电喷涂等方式设置在中间膜上；When the positive electrode layer has a single-layer or multi-layer structure, as mentioned above, it can be dry-pressed on the intermediate film in the order of the laminated structure. Dry spraying, dry electrostatic spraying, etc. are arranged on the interlayer;
除此之外，为得到厚度更薄的电池膜，亦可将靠近中间膜的功能层以浆料的方式依次涂覆干燥，其中，涂覆方式可以列举的有挤压涂布、转移涂布、(微)凹版涂布、喷涂、浸涂及线棒涂布、离子溅射、PVD、CVD、丝网印刷等。例如，当正极层的结构为正极活性层、正极导电层、正极粘结层的多层时，采用在线涂布的方式，在中间膜定型路线上依次挤压涂布正极粘结层浆料、正极导电层浆料、正极活性层浆料并依序干燥，最后成膜。In addition, in order to obtain a battery film with a thinner thickness, the functional layers close to the intermediate film can also be sequentially coated and dried in the form of slurry. Among them, the coating methods can be listed as extrusion coating and transfer coating. , (micro) gravure coating, spray coating, dip coating and wire rod coating, ion sputtering, PVD, CVD, screen printing, etc. For example, when the structure of the positive electrode layer is a multi-layered positive electrode active layer, a positive electrode conductive layer, and a positive electrode adhesive layer, in-line coating is used to sequentially extrude and coat the positive electrode adhesive layer slurry, The positive electrode conductive layer slurry and the positive electrode active layer slurry are sequentially dried, and finally a film is formed.
1.2 中间膜 1.2 Intermediate film
1.2.1 结构与材料 1.2.1 Structure and Materials
中间膜可为单层或多层，是用于支撑或分隔储能器件正、负极的功能层，中间膜依据储能器件的类型，可以为多孔膜或固态电解质膜、半固态电解质膜中的一种。The intermediate film can be single-layer or multi-layer, and is a functional layer used to support or separate the positive and negative electrodes of the energy storage device. A sort of.
当中间膜为多孔膜时，可以为单层或多层多孔基膜，可以列举的至少有聚烯烃、PET等，亦可以在多孔基膜的基础上至少一侧涂覆有有机或无机涂层，关于有机、无机涂层，可以列举的材料至少有无机氧化物、无机盐、聚酰亚胺、PVDF、聚酯等；其中，无机氧化物可以列举的有氧化铝、勃母石、Mg/Al/Be/Si等金属氧化物；在中间膜为涂布膜时，涂布膜的涂布方式可以为 凹版涂布、喷涂、浸涂、线棒涂布、刮涂、喷涂和辊涂、丝网印刷、在线涂布等任意一种。When the intermediate film is a porous film, it can be a single-layer or multi-layer porous base film, at least polyolefin, PET, etc. can be listed, and at least one side of the porous base film can be coated with an organic or inorganic coating , Regarding organic and inorganic coatings, the materials that can be listed are at least inorganic oxides, inorganic salts, polyimide, PVDF, polyester, etc.; among them, inorganic oxides can be listed as alumina, boehmite, Mg/ Metal oxides such as Al/Be/Si; when the intermediate film is a coating film, the coating method of the coating film can be gravure coating, spray coating, dip coating, wire bar coating, blade coating, spray coating and roll coating, Any one of screen printing, online coating, etc.
其中，这里的在线涂布是指，相较于传统涂布膜将多孔基膜制备工艺和涂布工分割为两个独立的程序或产线，在线涂布在多孔基膜初步微干后即进行涂布，涂层与多孔基膜同时干燥定型，二者之间可以相互调控，不但省去多孔基膜热定型、收卷等步骤，得到的中间膜厚度、孔隙率、一致性更好，与正极层的结合力更高强。Among them, the online coating here means that compared with the traditional coating film, the porous base film preparation process and the coating process are divided into two independent procedures or production lines. After coating, the coating and the porous base film are dried and shaped at the same time, and the two can be mutually regulated, which not only saves the steps of heat setting and winding of the porous base film, but also obtains better thickness, porosity and consistency of the intermediate film. The bonding force with the positive electrode layer is stronger.
当中间膜为固态电解质膜时，可以列举的种类至少有聚合物固态电解质、氧化物固态电解质、氧化物晶态固体电解质、LiPON型电解质、硫化物晶态固态电解质、硫化物玻璃及玻璃陶瓷固体电解质，可以列举的材料至少有聚氨酯、PEO、PAN、DOL、聚碳酸酯、PVDF、氮化锂、快离子导体材料，其中，快离子导体材料可以为钠离子、Mg离子、Zn离子、K离子、Al离子等一种或多种，如磷酸钛铝锂、锂镧锆氧、锂镧铊氧、。When the intermediate membrane is a solid electrolyte membrane, the types that can be listed are at least polymer solid electrolyte, oxide solid electrolyte, oxide crystalline solid electrolyte, LiPON type electrolyte, sulfide crystalline solid electrolyte, sulfide glass and glass ceramic solid Electrolyte, the materials that can be listed are at least polyurethane, PEO, PAN, DOL, polycarbonate, PVDF, lithium nitride, fast ion conductor material, wherein, fast ion conductor material can be sodium ion, Mg ion, Zn ion, K ion , Al ions, etc. one or more, such as lithium titanium aluminum phosphate, lithium lanthanum zirconium oxygen, lithium lanthanum thallium oxygen,.
1.2.2 制备工艺 1.2.2 Preparation process
当中间膜为多孔膜的时，至少可使用干法拉伸、湿法相分离、静电纺丝、抄纸工艺等工艺制得，特别的，中间膜为在多孔基膜的基础上至少一侧涂覆有有机或无机涂层时，中间膜可采用在线涂布工艺制得；当中间膜为固态电解质膜时，至少可以使用抄纸工艺、烧结、浇筑流延、静电纺丝等工艺制得。When the intermediate film is a porous film, at least it can be prepared by dry stretching, wet phase separation, electrospinning, papermaking and other processes. In particular, the intermediate film is at least one side of the porous base film. When coated with an organic or inorganic coating, the intermediate membrane can be prepared by an online coating process; when the intermediate membrane is a solid electrolyte membrane, it can be prepared at least by processes such as papermaking, sintering, casting and casting, and electrospinning. .
1.3 负极层 1.3 Negative layer
1.3.1 结构与材料 1.3.1 Structure and Materials
负极层可以为单层或多层，其是做为膜层干压在中间膜的一侧或做为涂层涂覆在中间膜一侧的功能层。The negative electrode layer can be a single layer or a multi-layer, which is a functional layer that is dry-pressed on one side of the intermediate film as a film layer or coated on one side of the intermediate film as a coating.
负极层可以为负极集流体层，相比现有技术，无负极活性材料可提高储能器件能量密度，达到减小储能器件厚度，降低成本的目的。The negative electrode layer can be a negative electrode current collector layer. Compared with the prior art, without the negative electrode active material, the energy density of the energy storage device can be improved, and the purpose of reducing the thickness of the energy storage device and reducing the cost is achieved.
除此之外，负极层可以为负极活性材料和导电剂、粘结剂混合后形成的均匀单层；负极活性材料和导电剂、粘结剂混合后各组分以重量比计，最优比例区间为：90:5:5～99:0.5:0.5，其中，负极活性材料至少可列举有碳材料、硅基材料，碳材料至少可列举有天然石墨、人造石墨、硬碳、中间相碳微球、石墨烯。In addition, the negative electrode layer can be a uniform monolayer formed by mixing the negative electrode active material, the conductive agent and the binder; after the negative electrode active material is mixed with the conductive agent and the binder, each component is based on the weight ratio, and the optimal ratio is The interval is: 90:5:5～99:0.5:0.5, among which, the negative electrode active material can at least include carbon materials and silicon-based materials, and the carbon materials can at least include natural graphite, artificial graphite, hard carbon, and mesophase carbon microstructure. Balls, Graphene.
负极层亦可以为靠近中间膜依次包括负极活性层、负极粘结层的多层，或者更进一步，负极层亦可以为靠近中间膜依次包括负极活性层、负极导电层、负极粘结层的多层，也可以为靠近中间膜由内至外依次包括负极粘结层，负极活性层，负极导电层。The negative electrode layer can also be a multi-layer that includes a negative electrode active layer and a negative electrode bonding layer in turn near the intermediate film, or further, the negative electrode layer can also be a multi-layer that includes a negative electrode active layer, a negative electrode conductive layer, and a negative electrode bonding layer in turn adjacent to the intermediate film. The layer can also include a negative electrode bonding layer, a negative electrode active layer, and a negative electrode conductive layer in sequence from the inside to the outside near the intermediate film.
上述粘结剂或负极粘结剂可列举的至少有PVDF、PVDF-HFP、SBR、丙烯酸酯、PAA、聚氨酯中的任意一种或组合。The above-mentioned binder or negative electrode binder may include at least any one or a combination of PVDF, PVDF-HFP, SBR, acrylate, PAA, and polyurethane.
电池膜的具体结构，可为上述各层结构方案的任意组合或搭配。The specific structure of the battery film can be any combination or combination of the above-mentioned layer structure schemes.
1.3.2 制备工艺 1.3.2 Preparation process
当负极层为单层或多层结构时，如前述，可按照层叠结构顺序干压至中间膜上，其中干压可以是在一定温度下施加压力，温度范围为0～90℃，也可以采用干喷法、干法静电喷涂等方式设置在中间膜上；When the negative electrode layer has a single-layer or multi-layer structure, as mentioned above, it can be dry-pressed on the intermediate film in the order of the laminated structure. Dry spraying, dry electrostatic spraying, etc. are arranged on the interlayer;
除此之外，为得到厚度更薄的电池膜，亦可将靠近中间膜的功能层以浆料的方式依次涂覆干燥，其中，涂覆方式可以列举的有挤压涂布、转移涂布、(微)凹版涂布、喷涂、浸涂及线棒涂布、离子溅射、PVD、CVD、蒸镀、磁控溅射、真空镀等。例如，当负极层的结构为负极活性层、负极导电层、 负极粘结层的多层时，采用在线涂布的方式，在中间膜定型路线上依次挤压涂布负极粘结层浆料、负极导电层浆料、负极活性层浆料并依次干燥，最后成膜。In addition, in order to obtain a battery film with a thinner thickness, the functional layers close to the intermediate film can also be sequentially coated and dried in the form of slurry. Among them, the coating methods can be listed as extrusion coating and transfer coating. , (micro) gravure coating, spray coating, dip coating and wire rod coating, ion sputtering, PVD, CVD, evaporation, magnetron sputtering, vacuum plating, etc. For example, when the structure of the negative electrode layer is a multilayer of the negative electrode active layer, the negative electrode conductive layer, and the negative electrode adhesive layer, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, the negative electrode adhesive layer slurry, The negative electrode conductive layer slurry and the negative electrode active layer slurry are sequentially dried, and finally a film is formed.
2. 电池膜的制备工艺 2. Preparation process of battery film
对于上述高能量密度的电池膜的制备方法，只要可获得具有上述结构的电池膜即可，没有特别限定。The method for producing the above-mentioned high-energy-density battery film is not particularly limited as long as a battery film having the above-mentioned structure can be obtained.
但是为得到一致性更好、结合力更强的电池膜，本发明提供一种制备工艺，依次包括：中间膜定型、中间膜在线涂布、电池膜定型。However, in order to obtain a battery film with better consistency and stronger binding force, the present invention provides a preparation process, which sequentially includes: forming the intermediate film, on-line coating of the intermediate film, and forming the battery film.
上述定型可能常温定型、低温定性、辐射定型、加压定型、化学或电化学反应固化定型中的任意一种。The above setting may be any one of normal temperature setting, low temperature setting, radiation setting, pressure setting, chemical or electrochemical reaction curing setting.
具体的，例如，制备工艺依次包括：中间膜热定型、中间膜在线涂布、电池膜热定型。在中间膜的定型的过程中，按照电池膜由内向外的层叠结构，将正极层浆料或负极层浆料依序设置在中间膜两侧后，中间膜热定型与涂层逐层干燥同步进行，形成电池膜一体式的生产流程与技术，有效提高生产效率，降低生产成本，相比在中间膜成型后再涂覆在中间膜两侧，采用该工艺能够缩短生产时长，得到的电池膜一致性更好，涂层与中间膜的结合力更强，界面阻抗水平优良，柔性更好，形状和尺寸灵活多高。Specifically, for example, the preparation process sequentially includes: heat setting of the intermediate film, on-line coating of the intermediate film, and heat setting of the battery film. In the process of setting the intermediate film, according to the laminated structure of the battery film from the inside to the outside, after the slurry of the positive electrode layer or the slurry of the negative electrode layer is sequentially arranged on both sides of the intermediate film, the thermal setting of the intermediate film and the drying of the coating layer by layer are synchronized. It can effectively improve production efficiency and reduce production costs. Compared with coating on both sides of the intermediate film after the intermediate film is formed, this process can shorten the production time, and the obtained battery film The consistency is better, the bonding force between the coating and the interlayer is stronger, the interface impedance level is excellent, the flexibility is better, and the shape and size are more flexible.
3. 电池膜的制备系统 3. Preparation system of battery film
上述涂布工艺对应有电池隔膜的涂布系统，包括：在中间膜定型的行进路线中设置有多个的膜定型装置，相邻膜定型装置的间隔位置设置有用于中间膜涂覆浆料的涂布装置。The above-mentioned coating process corresponds to a coating system for a battery separator, including: a plurality of film setting devices are arranged in the traveling route of the intermediate film setting, and a spacer for the intermediate film coating slurry is arranged at the interval position of the adjacent film setting devices. coating device.
膜定型装置、涂布装置不做特殊限制，可依据制备工艺、正极层或负极 层的层叠结构进行数量或类型的选择。The membrane setting device and coating device are not particularly limited, and the number or type can be selected according to the preparation process and the stacking structure of the positive electrode layer or the negative electrode layer.
例如：在中间膜热定型的行进路线中设置有多节的烘箱，相邻烘箱的间隔位置设置有用于中间膜涂覆浆料的涂布装置。For example, a multi-section oven is provided in the traveling route of the heat-setting of the interlayer, and a coating device for coating slurry of the interlayer is provided at the interval between adjacent ovens.
具体的，沿着中间膜定型的行进路线，设置有一组或多组连续设置的小组，每个小组包括涂布装置、位于涂布装置上游用于初步干燥中间膜的初步热定型烘箱、位于涂布装置下游用于干燥电池膜的涂布热定型烘箱，多组连续设置时，烘箱数目可根据实际需求减少或增设。Specifically, along the traveling route of the interlayer film setting, one or more groups of continuously arranged subgroups are provided, each subgroup includes a coating device, a preliminary heat setting oven located upstream of the coating device for preliminary drying of the interlayer film, The coating and heat-setting oven downstream of the cloth device is used for drying the battery film. When multiple groups are continuously set up, the number of ovens can be reduced or added according to actual needs.
4. 储能器件 4. Energy storage device
4.1 结构与材料 4.1 Structure and materials
本发明的储能器件包括但不限于锂离子电池、钠离子电池、镁离子电池、锌离子电池、固态电池、半固态电池、锂硫电池、液流电池领域，具体的，依次包括正极集流体、上述任意一项的电池膜、负极集流体；其中，正极集流体的材料至少有导电材料，导电材料优选Cu、AL、Ni；负极集流体的材料至少有导电材料或负极金属材料，负极金属材料优选锂金属、钠金属。The energy storage devices of the present invention include but are not limited to the fields of lithium ion batteries, sodium ion batteries, magnesium ion batteries, zinc ion batteries, solid-state batteries, semi-solid-state batteries, lithium-sulfur batteries, and flow batteries, and specifically, include positive electrode current collectors in sequence. , the battery film of any one of the above, the negative electrode current collector; wherein, the material of the positive electrode current collector at least has a conductive material, and the conductive material is preferably Cu, AL, Ni; the material of the negative electrode current collector has at least a conductive material or a negative electrode metal material, and the negative electrode metal The material is preferably lithium metal and sodium metal.
特别的，本发明电池膜在储能器件中使用时，尤其应用在固态电池或半固态领域时，相对于现有技术，因为界面阻抗更小原因，由本发明制备的储能器件，电解液非必要选项，仍能达到良好的倍率性能、低温充放电、长循环寿命效果。In particular, when the battery film of the present invention is used in an energy storage device, especially in the field of solid-state batteries or semi-solid state, compared with the prior art, the energy storage device prepared by the present invention has a lower interface impedance than the prior art. The necessary options can still achieve good rate performance, low temperature charge and discharge, and long cycle life.
另外，当电池膜的正极层为正极粘结层时，储能器件依次包括正极极片(包括正极集流体、正极活性材料)、电池膜、负极集流体。In addition, when the positive electrode layer of the battery film is the positive electrode bonding layer, the energy storage device sequentially includes a positive electrode sheet (including a positive electrode current collector and a positive electrode active material), a battery film, and a negative electrode current collector.
4.2 制备工艺 4.2 Preparation process
正极集流体、负极集流体与电池膜复合时，至少可采用离子溅射、PVD、 CVD、离线复合、贴合等方式。When the positive electrode current collector, the negative electrode current collector and the battery film are composited, at least ion sputtering, PVD, CVD, off-line composite, lamination and other methods can be used.
正负极的集流体与正负极膜复合也可以利用干电极技术，采用干喷或干粉静电喷涂工艺，得到正负极极片后再与中间膜复合得到对应的储能器件。The positive and negative current collectors and the positive and negative films can also be combined with the dry electrode technology, using dry spraying or dry powder electrostatic spraying technology to obtain the positive and negative electrode pieces and then compound with the intermediate film to obtain the corresponding energy storage device.
实施例Example
实施例一Example 1
采用厚度为9um的聚乙烯多孔隔膜，多孔隔膜的一侧用真空镀的方式设置一层厚度为10um的磷酸铁锂正极层形成电池膜，分别在电池膜的两侧设置铜箔和铝箔形成电化学器件，复合方式为层压复合，其中正极层侧复合铝箔，负极层侧复合铜箔。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件.A polyethylene porous diaphragm with a thickness of 9um is used, and a layer of lithium iron phosphate positive electrode layer with a thickness of 10um is formed on one side of the porous diaphragm by vacuum plating to form a battery film. For chemical devices, the compounding method is lamination compounding, wherein the anode layer side is compounded with aluminum foil, and the negative electrode layer side is compounded with copper foil. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例二 Embodiment 2
采用厚度为9um的聚乙烯多孔隔膜，多孔隔膜的一侧用在线涂布的方式设置一层厚度为80um的正极层形成电池膜，正极层由NCM、PVDF、导电炭以96:2:2组成，分别在电池膜的两侧设置铜箔和铝箔形成电化学器件，复合方式为层压复合，其中正极层侧复合铝箔，负极层侧复合铜箔。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A polyethylene porous membrane with a thickness of 9um is used. One side of the porous membrane is coated with a positive electrode layer with a thickness of 80um to form a battery film. The positive electrode layer is composed of NCM, PVDF and conductive carbon in a ratio of 96:2:2. , copper foil and aluminum foil are respectively arranged on both sides of the battery film to form an electrochemical device. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例三 Embodiment 3
采用厚度为12um的聚丙烯多孔隔膜，多孔隔膜的一侧用在线涂布的方式设置一层厚度为2um的PVDF层和80um的正极层形成电池膜，分别在电池膜的两侧设置铜箔和铝箔形成电化学器件，正极集流体与正极层通过涂布在正极层上的PVDF层复合，负极集流体复合方式为层压复合，其中正极层侧复合铝箔，负极层侧复合铜箔。上述结构依次层叠形成厚度35mm,长度40mm, 宽度90mm的储能器件。A polypropylene porous membrane with a thickness of 12um is used. One side of the porous membrane is coated with a PVDF layer with a thickness of 2um and a positive electrode layer with a thickness of 80um to form a battery membrane. The aluminum foil forms an electrochemical device. The positive electrode current collector and the positive electrode layer are composited through the PVDF layer coated on the positive electrode layer. The composite method of the negative electrode current collector is lamination composite, wherein the positive electrode layer side is composited with aluminum foil, and the negative electrode layer side is composited with copper foil. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例四 Embodiment 4
采用厚度为12um的聚丙烯多孔隔膜，多孔隔膜的一侧用真空镀的方式设置一层厚度为10um的NCM正极层，再涂覆PVDF层后形成电池膜，分别在电池膜的两侧设置铜箔和铝箔形成电化学器件，正极集流体与正极层通过涂布在正极层上的PVDF层复合，负极集流体复合方式为层压复合，其中正极层侧复合铝箔，负极层侧复合铜箔。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A polypropylene porous membrane with a thickness of 12um is used. One side of the porous membrane is vacuum-plated with an NCM positive electrode layer with a thickness of 10um, and then a PVDF layer is applied to form a battery film. The foil and the aluminum foil form an electrochemical device. The positive electrode current collector and the positive electrode layer are composited by the PVDF layer coated on the positive electrode layer. The composite method of the negative electrode current collector is lamination composite, wherein the positive electrode layer side is composited with aluminum foil, and the negative electrode layer side is composited with copper foil. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例五Embodiment 5
采用厚度为9um的聚乙烯多孔隔膜，多孔隔膜的一侧用真空镀的方式设置一层厚度为10um的NCM正极层，在正极侧依次涂覆导电炭层和PVDF层后形成电池膜，然后电池膜复合正极集流体和负极集流体，其中正极层侧复合铝箔，负极层侧复合铜箔。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A polyethylene porous membrane with a thickness of 9um is used. One side of the porous membrane is vacuum-plated with an NCM positive electrode layer with a thickness of 10um. A conductive carbon layer and a PVDF layer are sequentially coated on the positive electrode side to form a battery film. Then the battery The film composites the positive electrode current collector and the negative electrode current collector, wherein the positive electrode layer side is composited with aluminum foil, and the negative electrode layer side is composited with copper foil. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例六Embodiment 6
采用厚度为9um的聚乙烯多孔隔膜，多孔隔膜的一侧采用在线涂布的方式依次设置一层PMMA涂层和厚度为10um的NCA正极层，在正极层侧通过在线涂布的的方式依次涂覆导电炭层和PVDF层，形成电池膜，然后复合正极集流体和负极集流体，其中正极层侧复合铝箔，负极层侧复合铜箔。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A polyethylene porous diaphragm with a thickness of 9um is used. One side of the porous diaphragm is sequentially provided with a layer of PMMA coating and a NCA positive electrode layer with a thickness of 10um by in-line coating. The conductive carbon layer and PVDF layer are coated to form a battery film, and then the positive electrode current collector and the negative electrode current collector are combined, wherein the positive electrode layer side is combined with aluminum foil, and the negative electrode layer side is combined with copper foil. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例七Embodiment 7
采用厚度为9um的聚乙烯多孔隔膜，多孔隔膜的一侧采用逐次在线涂布 的方式依次涂覆氧化铝涂层、LCO层、导电炭层和PVDF层，形成电池膜，然后复合正极集流体和负极集流体，其中正极层侧复合铝箔，负极层侧复合铜箔。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A polyethylene porous diaphragm with a thickness of 9um is used, and one side of the porous diaphragm is sequentially coated with an alumina coating, an LCO layer, a conductive carbon layer and a PVDF layer by successive online coating to form a battery film, and then the composite cathode current collector and A negative electrode current collector, wherein the positive electrode layer side is compounded with aluminum foil, and the negative electrode layer side is compounded with copper foil. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例八Embodiment 8
采用厚度为9um的聚乙烯多孔隔膜，多孔隔膜的一侧采用逐次在线涂布的方式依次涂覆氧化铝涂层、PVDF层和NCM层，多孔膜的另外一侧采用,在线涂布的方式涂布负极浆料，负极浆料由Si:SBR:导电炭90:5:5，形成电池膜，然后复合正极集流体和负极集流体，其中正极层侧复合铝箔，负极层侧复合铜箔。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A polyethylene porous membrane with a thickness of 9um is used. One side of the porous membrane is coated with alumina coating, PVDF layer and NCM layer by successive online coating. The other side of the porous membrane is coated by online coating. Cloth the negative electrode slurry, the negative electrode slurry is composed of Si:SBR:conductive carbon 90:5:5 to form a battery film, and then composite the positive electrode current collector and the negative electrode current collector, wherein the positive electrode layer side is composited with aluminum foil, and the negative electrode layer side is composited with copper foil. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例九Embodiment 9
采用厚度为20um的LLZTO层，在LLZTO的一侧采用真空镀的方式设置厚度为10um的NCM，形成电池膜，然后复合正极集流体和负极集流体，其中正极层侧复合铝箔，负极层侧复合Li金属。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A LLZTO layer with a thickness of 20 um is used, and an NCM with a thickness of 10 um is set on one side of the LLZTO by vacuum plating to form a battery film, and then the positive electrode current collector and the negative electrode current collector are compounded, wherein the positive electrode layer side is compounded with aluminum foil, and the negative electrode layer side is compounded Li metal. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例十Embodiment ten
采用厚度为20um的LGPS层，在LGPS的一侧采用真空镀的方式设置厚度为10um的NCM，然后在NCM的另一侧涂覆PVDF，形成电池膜，分别在征集侧和负极侧复合正极集流体和负极集流体，其中正极层侧复合铝箔，负极层侧复合Li金属。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。The LGPS layer with a thickness of 20um is used, and the NCM with a thickness of 10um is set on one side of the LGPS by vacuum plating, and then PVDF is coated on the other side of the NCM to form a battery film. Fluid and negative electrode current collector, wherein the positive electrode layer side is compounded with aluminum foil, and the negative electrode layer side is compounded with Li metal. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例十一Embodiment 11
采用厚度为20um的PEO层，在PEO的一侧逐次涂覆厚度为10um的磷酸铁锂层、导电炭层和PVDF层，形成电池膜，分别在正极侧和负极侧复合正极集流体和负极集流体，其中正极层侧复合铝箔，负极层侧复合Li金属。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A PEO layer with a thickness of 20 um is used, and a layer of lithium iron phosphate, a conductive carbon layer and a PVDF layer with a thickness of 10 um are successively coated on one side of the PEO to form a battery film. Fluid, wherein the positive layer side is compounded with aluminum foil, and the negative electrode layer side is compounded with Li metal. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例十二Embodiment 12
采用厚度为9um的聚乙烯多孔隔膜，多孔隔膜的一侧采用逐次在线涂布的方式依次涂覆氧化铝涂层、多元Fe基过渡金属氧化Na层、导电石墨烯层和PVDF层，在多孔隔膜的另一侧通过在线涂覆依次涂覆硬碳等、导电炭层和SBR层，形成电池膜，然后两侧均复合铝箔集流体。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A polyethylene porous diaphragm with a thickness of 9um is used, and one side of the porous diaphragm is sequentially coated with alumina coating, multi-element Fe-based transition metal Na oxide layer, conductive graphene layer and PVDF layer by successive online coating. The other side of the battery is coated with hard carbon, etc., conductive carbon layer and SBR layer in turn by in-line coating to form a battery film, and then both sides are compounded with aluminum foil current collectors. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例十三Embodiment thirteen
采用厚度为20um的PEO膜，PEO膜的一侧采用逐次在线涂布的方式依次涂覆多元Fe基过渡金属氧化Na层、导电炭层和PVDF层，在PEO膜的另一侧涂覆硬碳层，形成电池膜，然后两侧均复合铝箔集流体。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A PEO film with a thickness of 20um is used. One side of the PEO film is coated with a multi-element Fe-based transition metal Na oxide layer, a conductive carbon layer and a PVDF layer by successive online coating, and hard carbon is coated on the other side of the PEO film. layer to form a battery film, and then composite aluminum foil current collectors on both sides. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例十四Embodiment 14
采用厚度为9um的聚乙烯多孔隔膜，多孔隔膜的一侧采用逐次在线涂布的方式依次涂覆氧化铝涂层、多元Mn基过渡金属氧化Na层、导电石墨烯层和PVDF层，在多孔隔膜的另一侧涂覆硬碳层，形成电池膜，然后两侧均复合铝箔集流体。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A polyethylene porous diaphragm with a thickness of 9um is used, and one side of the porous diaphragm is sequentially coated with alumina coating, multi-component Mn-based transition metal Na oxide layer, conductive graphene layer and PVDF layer by successive online coating. The other side is coated with a hard carbon layer to form a battery film, and then both sides are compounded with aluminum foil current collectors. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例十五Embodiment fifteen
采用厚度为20um的PEO膜，PEO膜的一侧采用逐次在线涂布的方式依次涂覆多元Fe基过渡金属氧化Na层、导电石墨烯层和PVDF层，形成电池膜，然后两侧均复合集流体，正极侧复合Al集流体，负极侧复合Na金属集流体。上述结构依次层叠形成厚度35mm,长度40mm,宽度90mm的储能器件。A PEO film with a thickness of 20um was used, and one side of the PEO film was sequentially coated with a multi-element Fe-based transition metal Na oxide layer, a conductive graphene layer and a PVDF layer by successive online coating to form a battery film, and then both sides were composited and collected. Fluid, the positive side is compounded with Al current collector, and the negative side is compounded with Na metal current collector. The above structures are stacked in sequence to form an energy storage device with a thickness of 35 mm, a length of 40 mm and a width of 90 mm.
实施例十六Embodiment 16
与实施例二步骤相同，不同之处在于：正极层由NCM、PVDF、导电炭以重量比90:5:5组成。The steps are the same as those in the second embodiment, except that the positive electrode layer is composed of NCM, PVDF, and conductive carbon in a weight ratio of 90:5:5.
实施例十七Embodiment seventeen
与实施例二步骤相同，不同之处在于：正极层由NCM、PVDF、导电炭以重量比99:0.5:0.5组成。The steps are the same as those in the second embodiment, except that the positive electrode layer is composed of NCM, PVDF, and conductive carbon in a weight ratio of 99:0.5:0.5.
实施例十八Embodiment 18
与实施例八步骤相同，不同之处在于：负极浆料由Si:SBR:导电炭以质量比99:0.5:0.5组成。The steps are the same as those in the eighth embodiment, except that the negative electrode slurry is composed of Si:SBR:conductive carbon in a mass ratio of 99:0.5:0.5.
实施例十九Example 19
与实施例八步骤相同，不同之处在于：负极浆料由Si:SBR:导电炭以质量比95:2.5:2.5组成。The steps are the same as those in the eighth embodiment, except that the negative electrode slurry is composed of Si:SBR:conductive carbon in a mass ratio of 95:2.5:2.5.
测试方法testing method
阻抗：将电池膜的正负极分别连接到电化学工作站的正负极上，选择电化学阻抗测试项目，设置扰动电压为10mV,频率范围是0.01Hz～1000000Hz,记录其阻抗值。Impedance: Connect the positive and negative electrodes of the battery membrane to the positive and negative electrodes of the electrochemical workstation, select the electrochemical impedance test item, set the disturbance voltage to 10mV, and the frequency range to 0.01Hz to 1,000,000Hz, and record the impedance value.
中间膜与正极层的剥离力：采用3M胶带分别贴在中间层和正极层两侧，并将样品裁成15mm宽，分别用万能拉伸试验机采用180°的方向拉伸两片 3M胶带，拉伸速度是50m/min,记录最大剥离力。Peeling force between the intermediate film and the positive electrode layer: 3M tape was used to stick on both sides of the intermediate layer and the positive electrode layer, respectively, and the sample was cut into a 15mm width, and two pieces of 3M tape were stretched in the direction of 180° with a universal tensile testing machine, respectively. The tensile speed was 50 m/min and the maximum peel force was recorded.
电池膜的能量密度：采用0.5C电流进行充放电，记录电池膜的放电容量C和电压平台V对电池膜进行称重记录为M，能量密度计算公式为C*V/M,并将单位换算成Wh/kg。The energy density of the battery film: charge and discharge with 0.5C current, record the discharge capacity C of the battery film and the voltage platform V, weigh the battery film and record it as M, the energy density calculation formula is C*V/M, and convert the unit. into Wh/kg.
电池膜的可弯折性：两手分别握住电池膜的头尾两端并轻轻对折，如果弯折角度超过45℃后可恢复原状，记为可弯折，否则记为不可弯折。Bendability of the battery film: Hold the head and tail ends of the battery film with both hands and gently fold them in half. If the bending angle exceeds 45°C, it can be restored to its original state, which is recorded as bendable, otherwise it is recorded as not bendable.
将实施例一至十九制备的电池膜、储能器件，在相同测试环境下，进行上述性能测试，并将性能数据记录在下表1中。The battery films and energy storage devices prepared in Examples 1 to 19 were subjected to the above performance tests under the same test environment, and the performance data were recorded in Table 1 below.
Figure PCTCN2022085955-appb-000001
Figure PCTCN2022085955-appb-000001
通过实施例一至十九可知，本发明提供的电池膜能够直接与正极集流体、负极集流体压制复合，得到储能器件，且在储能器件的内阻和能量密度保持目前行业技术领先的水平，能够推动目前储能器件生产流程改进与发展；且更进一步通过在线涂布的生产方式，简化电池膜的生产流程与步骤，得到的电池膜一致性更好，涂层与中间膜的结合力更强，界面阻抗保持优良水平，柔性更好。It can be seen from Examples 1 to 19 that the battery film provided by the present invention can be directly pressed and compounded with the positive electrode current collector and the negative electrode current collector to obtain an energy storage device, and the internal resistance and energy density of the energy storage device maintain the leading level of the current industry technology , which can promote the improvement and development of the current energy storage device production process; and further simplify the production process and steps of the battery film through the on-line coating production method, and the obtained battery film has better consistency and the bonding force between the coating and the intermediate film. Stronger, the interface impedance maintains an excellent level, and the flexibility is better.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明构思的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the concept of the present invention, several improvements and modifications can also be made, and these improvements and modifications should also be regarded as It is the protection scope of the present invention.

Claims (17)

  1. 一种储能器件用电池膜，其特征在于，依次包括正极层、中间膜。A battery film for an energy storage device is characterized in that it includes a positive electrode layer and an intermediate film in sequence.
  2. 如权利要求1所述的储能器件用电池膜，其特征在于，依次包括正极层、中间膜、负极层。The battery film for an energy storage device according to claim 1, characterized in that it comprises a positive electrode layer, an intermediate film, and a negative electrode layer in sequence.
  3. 如权利要求1所述的储能器件用电池膜，其特征在于，所述正极层包括正极活性层。The battery film for an energy storage device according to claim 1, wherein the positive electrode layer comprises a positive electrode active layer.
  4. 如权利要求1所述的储能器件用电池膜，其特征在于，所述正极层包括正极粘结层。The battery film for an energy storage device according to claim 1, wherein the positive electrode layer comprises a positive electrode bonding layer.
  5. 如权利要求1所述的储能器件用电池膜，其特征在于，所述正极层靠近中间膜依次包括正极活性层、正极粘结层，或，正极活性层、正极导电层、正极粘结层，或，正极粘结层、正极活性层，正极导电层。The battery film for an energy storage device according to claim 1, wherein the positive electrode layer adjacent to the intermediate film sequentially comprises a positive electrode active layer, a positive electrode adhesive layer, or a positive electrode active layer, a positive electrode conductive layer, and a positive electrode adhesive layer. , or, the positive electrode bonding layer, the positive electrode active layer, and the positive electrode conductive layer.
  6. 如权利要求3所述的储能器件用电池膜，其特征在于，所述正极活性层包括正极活性材料、导电剂、粘结剂。The battery film for an energy storage device according to claim 3, wherein the positive electrode active layer comprises a positive electrode active material, a conductive agent, and a binder.
  7. 如权利要求1所述的储能器件用电池膜，其特征在于，所述中间膜包括多孔膜、半固态电解质膜、固态电解质膜中的任意一种。The battery membrane for an energy storage device according to claim 1, wherein the intermediate membrane comprises any one of a porous membrane, a semi-solid electrolyte membrane, and a solid electrolyte membrane.
  8. 如权利要求7所述的储能器件用电池膜，其特征在于，所述多孔膜包括多孔基膜，或，多孔基膜以及在多孔基膜至少一侧的有机或无机涂层。The battery film for an energy storage device according to claim 7, wherein the porous film comprises a porous base film, or a porous base film and an organic or inorganic coating on at least one side of the porous base film.
  9. 如权利要求2所述的储能器件用电池膜，其特征在于，所述负极层包括负极粘结层。The battery film for an energy storage device according to claim 2, wherein the negative electrode layer comprises a negative electrode binding layer.
  10. 如权利要求2所述的储能器件用电池膜，其特征在于，所述负极层靠近中间膜依次包括负极活性层、负极粘结层，或，负极活性层、负极导电层、负极粘结层或，负极粘结层，负极活性层，负极导电层。The battery film for an energy storage device according to claim 2, wherein the negative electrode layer adjacent to the intermediate film sequentially comprises a negative electrode active layer, a negative electrode adhesive layer, or a negative electrode active layer, a negative electrode conductive layer, and a negative electrode adhesive layer. Or, the negative electrode bonding layer, the negative electrode active layer, and the negative electrode conductive layer.
  11. 如权利要求2所述的储能器件用电池膜，其特征在于，所述负极层 包括负极活性材料、导电剂、粘结剂。The battery film for an energy storage device according to claim 2, wherein the negative electrode layer comprises a negative electrode active material, a conductive agent, and a binder.
  12. 一种储能器件，其特征在于，依次包括正极集流体、权利要求1-3、5-10任意一项所述的电池膜、负极集流体。An energy storage device, characterized in that it comprises a positive electrode current collector, the battery film according to any one of claims 1-3 and 5-10, and a negative electrode current collector in sequence.
  13. 一种储能器件，其特征在于，依次包括正极极片、权利要求4所述的电池膜、负极集流体。An energy storage device, characterized in that it includes a positive electrode plate, the battery film according to claim 4, and a negative electrode current collector in sequence.
  14. 一种储能器件用电池膜的制备工艺，其特征在于，依次包括：中间膜定型、中间膜在线涂布、电池膜定型。A preparation process of a battery film for an energy storage device, which is characterized in that the steps include: forming an intermediate film, on-line coating of the intermediate film, and forming a battery film.
  15. 如权利要求14所述的储能器件用电池膜的制备工艺，其特征在于，依次包括：中间膜热定型、中间膜在线涂布、电池膜热定型。The preparation process of a battery film for an energy storage device according to claim 14, characterized in that, it comprises in sequence: heat setting of the intermediate film, on-line coating of the intermediate film, and heat setting of the battery film.
  16. 一种储能器件用电池膜的制备系统，包括：在中间膜定型的行进路线中设置有多个的膜定型装置，相邻膜定型装置的间隔位置设置有用于中间膜涂覆浆料的涂布装置。A preparation system for a battery film for an energy storage device, comprising: a plurality of film shaping devices are arranged in the traveling route of the intermediate film shaping, and a coating for the intermediate film coating slurry is arranged in the spaced position of the adjacent film shaping devices. cloth device.
  17. 如权利要求16所述的储能器件用电池膜的制备系统，其特征在于，包括：在中间膜热定型的行进路线中设置有多节的烘箱，相邻烘箱的间隔位置设置有用于中间膜涂覆浆料的涂布装置。The preparation system of a battery film for an energy storage device according to claim 16, characterized in that it comprises: a multi-section oven is arranged in the traveling route of the heat-setting of the intermediate film, and spaced positions between adjacent ovens are provided with an oven for the intermediate film Coating device for coating slurry.
PCT/CN2022/085955 2021-04-09 2022-04-08 Battery separator for energy storage device, preparation process thereof, preparation system therefor, and energy storage device WO2022214095A1 (en)

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