WO2025007595A1 - 聚噻吩导电聚合物、正极浆料、正极极片及其制备方法、电池单体、电池和用电装置 - Google Patents

聚噻吩导电聚合物、正极浆料、正极极片及其制备方法、电池单体、电池和用电装置 Download PDF

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WO2025007595A1
WO2025007595A1 PCT/CN2024/083548 CN2024083548W WO2025007595A1 WO 2025007595 A1 WO2025007595 A1 WO 2025007595A1 CN 2024083548 W CN2024083548 W CN 2024083548W WO 2025007595 A1 WO2025007595 A1 WO 2025007595A1
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positive electrode
optionally
battery
conductive polymer
binder
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French (fr)
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张昕晖
邢祁
刘会会
张振旭
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/139—Processes of manufacture
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/122—Copolymers statistical
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1422—Side-chains containing oxygen containing OH groups
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
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    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to a polythiophene conductive polymer, a positive electrode slurry, a positive electrode plate and a preparation method thereof, a battery cell, a battery and an electrical device.
  • the present application provides a polythiophene conductive polymer, a positive electrode slurry, a positive electrode plate and a preparation method thereof, a battery cell, a battery and an electrical device, which can enable the battery to have both high energy density and good rate performance.
  • the present application provides a polythiophene conductive polymer, comprising: a first structural unit represented by formula (1); and at least one of a second structural unit represented by formula (2), a third structural unit represented by formula (3), and a fourth structural unit represented by formula (4).
  • R 11 includes a C1-C8 alkyl group or a C1-C8 alkyl alkoxy group
  • R 12 includes a hydrogen atom or a C1-C3 alkyl group
  • R 21 includes a C1-C5 alkylene group
  • R 22 includes a hydrogen atom or a C1-C3 alkyl group
  • M includes a monovalent metal
  • R 31 includes a C1-C5 alkylene group
  • R 32 includes a hydrogen atom or a C1-C3 alkyl group
  • R 41 includes a C1-C5 alkylene group
  • R 42 includes a residue of a diisocyanate
  • R 43 includes a C2-C6 alkylene group
  • R 44 includes a C1-C3 alkyl group
  • R 45 includes a hydrogen atom or a C1-C3 alkyl group, s ⁇ 1; n1>0; n2 ⁇ 0, n3 ⁇ 0, n4 ⁇ 0, and n
  • the positive electrode plate include the polythiophene conductive polymer of the present application, the cohesion and adhesion of the positive electrode plate can be improved, the electrolyte wettability of the positive electrode plate can be improved, and the processing performance and dynamic performance of the positive electrode plate can be improved, thereby enabling the battery to have both high energy density and good rate performance.
  • the number average molecular weight of the polythiophene conductive polymer is 3000-45000, and can be 5000-34000.
  • the positive electrode sheet can have good flexibility, thereby improving the processing performance of the positive electrode sheet and the battery; in addition, the positive electrode slurry can also have good dispersibility, thereby better improving the performance of the battery.
  • the polythiophene conductive polymer satisfies at least one of the following conditions (1) to (13):
  • R 11 includes C4-C6 alkyl or C4-C6 alkylalkoxy
  • R 12 includes a hydrogen atom
  • R 21 includes C1-C3 alkylene
  • R 22 includes a hydrogen atom
  • M includes Li and/or Na
  • R 31 includes C1-C3 alkylene
  • R 32 includes a hydrogen atom
  • R 41 includes C1-C3 alkylene
  • R 42 includes Ra substituted or unsubstituted C1-C6 alkylene, and one of the following groups:
  • Ra independently includes C1-C3 alkyl
  • Rb independently includes C1-C3 alkyl
  • p represents an integer of 0-4
  • q represents an integer of 0-6;
  • R 43 includes the following groups:
  • R 44 includes a methyl group
  • R 45 includes a hydrogen atom
  • (13)s is 3-140, and can be optionally 10-90.
  • the second aspect of the present application provides a positive electrode slurry, comprising a solvent and a non-solvent component, wherein the non-solvent component comprises a positive electrode active material, a positive electrode binder and a positive electrode conductor, and the positive electrode conductor comprises the polythiophene conductive polymer of the first aspect of the present application.
  • the solvent includes a non-aqueous solvent, which may optionally include N-methylpyrrolidone, and the positive electrode binder includes an oily binder, and 0.35 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.65; optionally, 0.40 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.60.
  • n1/(n1+n2+n3+n4) is within the above range, the dispersibility of the non-aqueous positive electrode slurry can be improved, the processing performance of the prepared positive electrode sheet can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes one or more of polyvinylidene fluoride, polyimide, and polyurethane.
  • the positive electrode binder includes an oily binder, and 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.25, and optionally, 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.10. This can improve the dispersibility of the non-aqueous positive electrode slurry and improve the dynamic performance of the positive electrode sheet and the battery.
  • the positive electrode binder includes an oily binder, and 0.35 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.65, optionally, 0.40 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60.
  • the heating efficiency of the positive electrode sheet can be improved, the bonding force and cohesion of the positive electrode sheet can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an oily binder, and 0 ⁇ n4/(n3+n4) ⁇ 0.20, optionally, 0 ⁇ n4/(n3+n4) ⁇ 0.15.
  • n4/(n3+n4) is within the above range, the processing performance of the positive electrode sheet and the battery can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the solvent includes water
  • the positive electrode binder includes an aqueous binder, and 0.05 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.25; optionally, 0.08 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.22.
  • n1/(n1+n2+n3+n4) is within the above range, the dispersibility of the aqueous positive electrode slurry can be improved, the bonding force and processing performance of the prepared positive electrode sheet can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes one or more of carboxymethyl cellulose and its derivatives, sodium alginate, polyacrylic acid and its derivatives, agarose, gelatin, carrageenan, xanthan gum, guar gum, polyvinyl alcohol, and polyacrylamide.
  • the positive electrode binder includes an aqueous binder, and 0.15 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.45, optionally, 0.25 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.40.
  • n2/(n1+n2+n3+n4) is within the above range, the heating efficiency of the positive electrode sheet can be improved, the bonding force and cohesion of the positive electrode sheet can be enhanced, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder, and 0.30 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.80, optionally, 0.40 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60.
  • (n3+n4)/(n1+n2+n3+n4) is within the above range, the heating efficiency of the positive electrode sheet can be improved, the bonding force and cohesion of the positive electrode sheet can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder, and 0 ⁇ n4/(n3+n4) ⁇ 0.20, optionally, 0.04 ⁇ n4/(n3+n4) ⁇ 0.15.
  • n4/(n3+n4) is within the above range, the processing performance of the positive electrode sheet and the battery can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode active material includes one or more of lithium transition metal oxides, lithium-containing phosphates, and modified compounds thereof.
  • the positive electrode slurry further includes a second conductive agent, and the second conductive agent includes one or more of superconducting carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the content of the polythiophene conductive polymer in the non-solvent component is 0.2-4%, optionally 0.5-3%, based on the total weight of the non-solvent component.
  • the third aspect of the present application provides a positive electrode plate, including a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, the positive electrode film layer includes a positive electrode active material, a positive electrode binder and a positive electrode conductor, and the positive electrode conductor includes the polythiophene conductive polymer of the first aspect of the present application.
  • the positive electrode binder includes an oily binder, and 0.35 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.65; optionally, 0.40 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.60.
  • n1/(n1+n2+n3+n4) is within the above range, the uniformity of the positive electrode film layer can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes one or more of polyvinylidene fluoride, polyimide, and polyurethane.
  • the positive electrode binder includes an oily binder, and 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.25, optionally, 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.10. This can improve the uniformity of the positive electrode film layer and the dynamic performance of the positive electrode sheet and the battery.
  • the positive electrode binder includes an oily binder, and 0.35 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.65, optionally, 0.40 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60.
  • the heating efficiency of the positive electrode sheet can be improved, the bonding force and cohesion of the positive electrode sheet can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an oily binder, and 0 ⁇ n4/(n3+n4) ⁇ 0.20, optionally, 0 ⁇ n4/(n3+n4) ⁇ 0.15.
  • n4/(n3+n4) is within the above range, the processing performance of the positive electrode sheet and the battery can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder, and 0.05 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.25; optionally, 0.08 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.22.
  • n1/(n1+n2+n3+n4) is within the above range, the uniformity of the positive electrode film layer can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes one or more of carboxymethyl cellulose and its derivatives, sodium alginate, polyacrylic acid and its derivatives, agarose, gelatin, carrageenan, xanthan gum, guar gum, polyvinyl alcohol, and polyacrylamide.
  • the positive electrode binder includes an aqueous binder, and 0.15 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.45, optionally, 0.25 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.40.
  • n2/(n1+n2+n3+n4) is within the above range, the heating efficiency of the positive electrode sheet can be improved, the bonding force and cohesion of the positive electrode sheet can be enhanced, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder, and 0.30 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.80, optionally, 0.40 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60.
  • (n3+n4)/(n1+n2+n3+n4) is within the above range, the heating efficiency of the positive electrode sheet can be improved, the bonding force and cohesion of the positive electrode sheet can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder, and 0 ⁇ n4/(n3+n4) ⁇ 0.20, optionally, 0.04 ⁇ n4/(n3+n4) ⁇ 0.15.
  • n4/(n3+n4) is within the above range, the processing performance of the positive electrode sheet and the battery can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode active material includes one or more of lithium transition metal oxides, lithium-containing phosphates, and modified compounds thereof.
  • the positive electrode plate further includes a second conductive agent, which includes one or more of superconducting carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • a second conductive agent which includes one or more of superconducting carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the content of the polythiophene conductive polymer in the positive electrode film layer is 0.2-4%, optionally 0.5-3%, based on the total weight of the positive electrode film layer.
  • the fourth aspect of the present application provides a method for preparing a positive electrode sheet, comprising the following steps: coating the positive electrode slurry of the second aspect of the present application on at least one surface of the positive electrode collector, and obtaining an initial positive electrode sheet after drying and rolling; irradiating the initial positive electrode sheet obtained with a laser, and obtaining a positive electrode sheet after completion, wherein the laser wavelength is 445-505nm.
  • the polythiophene conductive polymer can be quickly heated, thereby releasing some stress, which is conducive to forming a positive electrode film layer with higher porosity, thereby reducing the amount of residual solvent and improving the electrolyte wettability of the positive electrode plate.
  • Blue light irradiation can also remove substances such as dispersants and surfactants introduced during the processing of the positive electrode plate.
  • the heating efficiency is high, and the heating temperature is usually higher than the softening point of the positive electrode binder, thereby allowing the positive electrode binder to be evenly distributed in the thickness direction of the positive electrode plate, thereby helping to improve the cohesion and adhesion of the positive electrode plate, reduce the positive electrode resistance, and thus improve the rate performance of the battery.
  • the laser is emitted in a continuous manner.
  • the number of lasers is 1-10, and the total power is 100-2500W.
  • the time for the initial positive electrode plate to pass through the laser spot is 0.05-0.5s.
  • the vertical distance between the laser and the initial positive electrode plate is 5-15 cm.
  • a fifth aspect of the present application provides a battery cell, comprising the positive electrode sheet of the third aspect of the present application or the positive electrode sheet prepared by the preparation method of the fourth aspect of the present application.
  • a sixth aspect of the present application provides a battery, comprising the battery cell of the fifth aspect of the present application.
  • the seventh aspect of the present application provides an electrical device, which includes the battery of the sixth aspect of the present application.
  • the electric device of the present application includes the battery provided by the present application, and thus has at least the same advantages as the battery.
  • FIG. 1 is a schematic diagram of the structure of a battery cell provided in some embodiments of the present application.
  • FIG. 2 is a schematic diagram of an exploded view of a battery cell provided in some embodiments of the present application.
  • FIG. 3 is a schematic diagram of the structure of a battery module provided in some embodiments of the present application.
  • FIG. 4 is a schematic diagram of the structure of a battery pack provided in some embodiments of the present application.
  • FIG. 5 is an exploded schematic diagram of the battery pack shown in FIG. 4 .
  • FIG. 6 is a schematic diagram of an electrical device provided in some embodiments of the present application.
  • FIG. 7 is a discharge curve of the battery of Example 1-1 and Comparative Example 1-1 at different rates.
  • “Scope” disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range.
  • the scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.
  • the numerical range "ab” represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers.
  • the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.
  • a parameter is expressed as an integer ⁇ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may further include step (c), which means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • the values of the parameters mentioned in this application can be measured by various test methods commonly used in the art, for example, they can be measured according to the test methods given in the examples of this application. Unless otherwise specified, the test temperature of each parameter is 25°C.
  • alkyl encompasses both straight chain and branched chain alkyl groups.
  • alkylene encompasses straight chain alkylene and branched chain alkylene.
  • alkylalkoxy encompasses straight chain alkylalkoxy and branched chain alkylalkoxy.
  • hydroxide encompasses1H(H),2H(D) and3H ( T ).
  • a single bond passes through a ring or a ring system means that the single bond can be attached to any accessible position of the ring or the ring system.
  • C1-C6 alkyl discloses C1, C2, C3, C4, C5, C6, C1-C6, C1-C5, C1-C4, C1-C3, C1-C2, C2-C6, C2-C5, C2-C4, C2-C3, C3-C6, C3-C5, C3-C4, C4-C6, C4-C5, C5-C6 alkyl individually.
  • the integer of 3-10 in the scope discloses 3,4,5,6,7,8,9 and 10 individually. Accordingingly, other groups or scopes can be clearly expected.
  • the battery mentioned in the embodiments of the present application may be a single physical module including one or more battery cells to provide higher voltage and capacity.
  • the battery mentioned in the present application may include a battery cell, a battery module or a battery pack.
  • a battery cell is the smallest unit of a battery, which can independently realize the functions of charging and discharging.
  • a battery cell can be cylindrical, rectangular, or in other shapes, etc., which is not limited in the present application.
  • FIG1 is a battery cell 5 of a rectangular structure as an example.
  • the battery can be a battery module; when there are multiple battery cells, the multiple battery cells are arranged and fixed to form a battery module.
  • the battery can be a battery pack, which includes a box and battery cells, and the battery cells or The battery module is housed in a box.
  • the box can be used as part of the chassis structure of the vehicle. For example, a portion of the box can become at least a portion of the floor of the vehicle, or a portion of the box can become at least a portion of the crossbeam and longitudinal beam of the vehicle.
  • the battery may be an energy storage device, which includes an energy storage container, an energy storage cabinet, and the like.
  • the battery cells provided in the embodiments of the present application include lithium-ion battery cells, lithium metal battery cells, etc., but the embodiments of the present application are not limited to this.
  • a battery cell generally includes an electrode assembly and an electrolyte.
  • the electrode assembly generally includes a positive electrode sheet and a negative electrode sheet.
  • the electrode assembly may be a wound structure or a laminated structure, which is not limited in the present application.
  • the battery cell may also include an outer package, which may be used to encapsulate the electrode assembly and the electrolyte.
  • the outer package may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer package may also be a soft package, such as a bag-type soft package.
  • the material of the soft package may be plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT) and polybutylene succinate (PBS).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PBS polybutylene succinate
  • the outer package may include a shell 51 and a cover plate 53.
  • the shell 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the shell 51 has an opening connected to the receiving cavity, and the cover plate 53 is used to cover the opening to close the receiving cavity.
  • the electrode assembly 52 is encapsulated in the receiving cavity.
  • the number of electrode assemblies 52 contained in the battery cell 5 can be one or more, which can be adjusted according to demand.
  • battery cells can be assembled into a battery module, and the number of battery cells contained in the battery module can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
  • FIG. 3 is a schematic diagram of a battery module 4 as an example. As shown in FIG. 3, in the battery module 4, multiple battery cells 5 can be arranged in sequence along the length direction of the battery module 4. Of course, they can also be arranged in any other manner. Further, the multiple battery cells 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having a receiving space, and the plurality of battery cells 5 are received in the receiving space.
  • the battery modules described above may also be assembled into a battery pack, and the number of battery modules contained in the battery pack may be adjusted according to the application and capacity of the battery pack.
  • FIG4 and FIG5 are schematic diagrams of a battery pack 1 as an example.
  • the battery pack 1 may include a box body and a plurality of battery modules 4 disposed in the box body.
  • the box body includes an upper box body 2 and a lower box body 3, and the upper box body 2 is used to cover the lower box body 3 and form a closed space for accommodating the battery modules 4.
  • the plurality of battery modules 4 can be arranged in the box body in any manner.
  • the positive electrode is an important component of the battery, and its performance has a crucial impact on the battery performance.
  • the current common practice is to prepare a thick-coated positive electrode sheet or a high-density positive electrode sheet.
  • the flexibility and processing performance of thick-coated and/or high-density positive electrode sheets are usually poor.
  • the positive electrode film layer is prone to cracking or part of the positive electrode film layer falls off from the surface of the positive electrode current collector (i.e., powder loss).
  • the residual solvent such as water, N-methylpyrrolidone, etc.
  • the residual solvent such as water, N-methylpyrrolidone, etc.
  • the inventors proposed a new polythiophene conductive polymer, which is used in the positive electrode. After light irradiation treatment, the processing performance of the positive electrode can be improved, and the battery can also have both high energy density and good rate performance.
  • the polythiophene conductive polymer provided in the embodiment of the present application includes a first structural unit represented by formula (1) and at least one of a second structural unit represented by formula (2), a third structural unit represented by formula (3) and a fourth structural unit represented by formula (4).
  • R 11 includes a C1-C8 alkyl group or a C1-C8 alkylalkoxy group
  • R 12 includes a hydrogen atom or a C1-C3 alkyl group.
  • R 21 includes a C1-C5 alkylene group
  • R 22 includes a hydrogen atom or a C1-C3 alkyl group
  • M includes a monovalent metal.
  • R 31 includes a C1-C5 alkylene group
  • R 32 includes a hydrogen atom or a C1-C3 alkyl group.
  • R 41 includes C1-C5 alkylene
  • R 42 includes the residue of diisocyanate
  • R 43 includes C2-C6 alkylene
  • R 44 includes C1-C3 alkyl
  • R 45 includes hydrogen atom or C1-C3 alkyl, s ⁇ 1.
  • the current common practice is to increase the amount of positive electrode conductive agent, such as conductive carbon, when preparing the positive electrode slurry, which can not only reduce the overall resistance of the positive electrode film layer, but also improve the rate performance of the battery.
  • positive electrode conductive agent such as conductive carbon
  • the dispersion uniformity of the conductive carbon deteriorates, so the above method has limited effect on improving the internal resistance and rate performance of the battery, and the processing performance of the positive electrode sheet and the battery is still relatively poor.
  • the inventors have found that by making the positive electrode plate include the polythiophene conductive polymer provided in the embodiments of the present application, the cohesion and adhesion of the positive electrode plate can be improved, the electrolyte wettability of the positive electrode plate can be improved, and the processing performance and dynamic performance of the positive electrode plate can be improved, thereby enabling the battery to have both high energy density and good rate performance.
  • the positive electrode active material in the positive electrode plate has a low absorption rate for blue light, while the polythiophene conductive polymer provided in the embodiment of the present application has a high blue light absorption capacity. Therefore, by using the polythiophene conductive polymer provided in the embodiment of the present application in the positive electrode plate and irradiating the positive electrode plate with blue light, rapid photothermal conversion can be performed, the heating efficiency can be improved, and the adverse effects of blue light irradiation on the positive electrode active material can be reduced.
  • the polythiophene conductive polymer provided in the embodiment of the present application has good thermal conductivity.
  • the polythiophene conductive polymer can be quickly heated, thereby releasing part of the stress, which is conducive to forming a positive electrode film layer with a high porosity, thereby reducing the amount of residual solvent and improving the electrolyte wettability of the positive electrode plate; when heated, the positive electrode binder can be softened, so that the polythiophene conductive polymer and the positive electrode binder are It is more evenly distributed in the positive electrode film layer, thereby increasing the cohesion and adhesion of the positive electrode sheet, and reducing the positive electrode resistance, thereby improving the dynamic performance of the positive electrode sheet and the battery.
  • the polythiophene conductive polymer provided in the embodiment of the present application includes at least one of the second structural unit shown in formula (2), the third structural unit shown in formula (3) and the fourth structural unit shown in formula (4), wherein the second structural unit shown in formula (2), the third structural unit shown in formula (3) and the fourth structural unit shown in formula (4) have strong polar groups, such as hydroxyl groups, ester groups, carbamate groups, etc. These strong polar groups can red-shift the absorption wavelength of the polythiophene conductive polymer, thereby reducing the electrochemical band gap between the HOMO orbit and the LUMO orbit, thereby increasing the position of the maximum absorption peak of the polythiophene conductive polymer and improving the heating efficiency.
  • strong polar groups such as hydroxyl groups, ester groups, carbamate groups, etc.
  • the polythiophene conductive polymer provided in the embodiment of the present application also includes the first structural unit shown in formula (1), thereby making the positive electrode film layer have good electrolyte wettability and preventing the polythiophene conductive polymer from dissolving.
  • the polythiophene conductive polymer provided in the embodiment of the present application can be used in the positive electrode film layer to improve the flexibility and processing performance of the positive electrode sheet, especially the positive electrode sheet with thick coating and/or high compaction density.
  • the polythiophene conductive polymer provided in the embodiment of the present application has conductivity and can provide a good electronic conductive path when used in the positive electrode sheet.
  • the polythiophene conductive polymer provided in the embodiment of the present application can improve the processing performance of the positive electrode plate, improve the cohesion and adhesion of the positive electrode plate, and can also reduce the positive electrode resistance.
  • a battery with both high energy density and good rate performance can be obtained.
  • the polythiophene conductive polymer provided in the embodiment of the present application includes a first structural unit represented by formula (1) and at least one of a second structural unit represented by formula (2), a third structural unit represented by formula (3) and a fourth structural unit represented by formula (4).
  • the number average molecular weight of the polythiophene conductive polymer can be 3000-45000, for example, 3000, 4000, 5000, 7600, 8600, 10000, 12000, 15000, 18000, 20500, 23000, 25200, 28000, 30000, 34000, 40000, 45000, or any range thereof.
  • the number average molecular weight of the polythiophene conductive polymer can be 5000-34000, 7600-34000, 10000-34000, 5000-30000, 7600-30000, 10000-30000, 5000-28000, 7600-28000, 10000-28000, 5000-25200, 7600-25200, 10000-25200.
  • the positive electrode sheet can have good flexibility, thereby improving the processing performance of the positive electrode sheet and the battery; in addition, the positive electrode slurry can have good dispersibility and the polythiophene conductive polymer can be prevented from dissolving in the electrolyte, thereby better improving the performance of the battery.
  • the polythiophene conductive polymer can also have good thermal conductivity and electronic conductivity, thereby improving the heating efficiency and reducing the positive electrode resistance.
  • the number average molecular weight of the polythiophene conductive polymer has a well-known meaning in the art and can be measured using instruments and methods known in the art, for example, by gel permeation chromatography (GPC).
  • R 11 may include a C4-C6 alkyl group or a C4-C6 alkylalkoxy group.
  • R 12 may include a hydrogen atom.
  • R 11 includes a C4-C6 alkyl group or a C4-C6 alkylalkoxy group
  • R 12 includes a hydrogen atom
  • R 21 may include a C1-C3 alkylene group.
  • R 22 may include a hydrogen atom.
  • M may include Li and/or Na.
  • R 21 includes a C1-C3 alkylene group
  • R 22 includes a hydrogen atom
  • M includes Li and/or Na.
  • R 31 may include a C1-C3 alkylene group.
  • R 32 may include a hydrogen atom.
  • R 31 includes a C1-C3 alkylene group
  • R 32 includes a hydrogen atom
  • R 41 may include a C1-C3 alkylene group.
  • R 42 may represent a residue of an aliphatic, alicyclic and/or aromatic diisocyanate.
  • R 42 includes Ra substituted or unsubstituted C1-C6 alkylene, and one of the following groups:
  • # represents the connection position
  • Ra independently includes C1-C3 alkyl
  • Rb independently includes C1-C3 alkyl
  • p represents an integer of 0-4
  • q represents an integer of 0-6. When p is 0, it means that the position is not substituted. When q is 0, it means that the position is not substituted.
  • R 43 may include the following groups:
  • R 44 can include a methyl group.
  • R 45 may include a hydrogen atom.
  • s can be 3-140, for example, 3, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or any range thereof.
  • s can be 10-90, 10-80, 10-70, 10-60, 10-50, 20-90, 20-80, 20-70, 20-60, 20-50, 25-90, 25-80, 25-70, 25-60, 25-50.
  • the present application also provides a method for preparing the polythiophene conductive polymer.
  • the method at least comprises the steps of: providing a monomer compound or a precursor compound for preparing a polythiophene conductive polymer; preparing the polythiophene conductive polymer by oxidative polymerization of the monomer compound or the precursor compound.
  • the oxidative polymerization method may be a chemical oxidative polymerization method or an electrochemical oxidative polymerization method.
  • the oxidant of the chemical oxidative polymerization method may be FeCl 3 .
  • the first monomer compound used to form the first structural unit can be any organic compound used to form the first structural unit.
  • the first monomer compound used to form the first structural unit can be any organic compound used to form the first structural unit.
  • the first monomer compound may include one or more of 3-butoxythiophene and 3-pentoxythiophene.
  • the first monomer compound can be obtained by alkyl chain replacement using methoxythiophene as a raw material.
  • methoxythiophene, alcohol (such as n-butanol, n-pentanol, etc.), anhydrous sodium bisulfate, and toluene are sequentially added to a reaction system in a nitrogen environment, heated and stirred at 80-100° C. for 2-5 hours, and the first monomer compound is obtained by reduced pressure distillation.
  • the second monomer compound used to form the second structural unit may be or its precursor compound R 23 includes a C1-C8 alkyl group.
  • the second monomer compound may include one or more of sodium thiophene-3-oxyacetate, lithium thiophene-3-oxyacetate, sodium 2-(thiophene-3-oxy)propionate, lithium 2-(thiophene-3-oxy)propionate, sodium 3-(thiophene-3-oxy)propionate, and lithium 3-(thiophene-3-oxy)propionate
  • the precursor compound of the second monomer compound may include one or more of methyl thiophene-3-oxyacetate, ethyl thiophene-3-oxyacetate, methyl 2-(thiophene-3-oxy)propionate, ethyl 2-(thiophene-3-oxy)propionate, methyl 3-(thiophene-3-oxy)propionate, and ethyl 3-(thiophene-3-oxy)propionate.
  • the precursor compound of the second monomer compound can be obtained by alkyl chain replacement using methoxythiophene as a raw material.
  • methoxythiophene, ester such as methyl glycolate, ethyl glycolate, methyl lactate, ethyl lactate, methyl ⁇ -hydroxypropionate, ethyl ⁇ -hydroxypropionate, etc.
  • anhydrous sodium bisulfate, and toluene are sequentially added to the reaction system and heated and stirred at 80-100° C. for 2-5 hours, and the precursor compound of the second monomer compound is obtained by reduced pressure distillation.
  • the second monomer compound can be prepared by placing a precursor compound of the second monomer compound in an alkaline solution, adjusting the pH, and stirring the solution to obtain the second monomer compound.
  • the alkaline solution can include MOH, and M includes a monovalent metal, which can be Li and/or Na.
  • the third monomer compound used to form the third structural unit can be any organic compound used to form the third structural unit.
  • the third monomer compound may include one or more of 3-thiophene methanol and 3-thiophene ethanol.
  • the fourth monomer compound used to form the fourth structural unit can be any monomer compound used to form the fourth structural unit.
  • the fourth monomer compound can be prepared by the following method: under nitrogen environment, OH—(R 43 ) s —O—R 44 and diisocyanate OCN—R 42 —NCO are dissolved in a solvent (such as N,N-dimethylformamide), stirred at 70° C. for 1-4 hours, and then added The reaction was continued at 70° C. with stirring for 4-8 hours under nitrogen protection to obtain a fourth monomer compound.
  • a solvent such as N,N-dimethylformamide
  • OH—(R 43 ) s —O—R 44 may include polyethylene glycol monomethyl ether (MPEG) and polybutylene glycol monomethyl ether.
  • the method comprises the steps of: dissolving a monomer compound or a precursor compound thereof in chloroform, then adding the monomer compound to a chloroform solution of anhydrous FeCl 3 under nitrogen protection, performing a polymerization reaction at 20-25° C. (e.g., 24-96 h), then adding methanol to precipitate the polymerization product, and finally extracting the precipitate in ethanol (e.g., 24-96 h), and obtaining a polythiophene conductive polymer after drying.
  • the method includes the steps of: dissolving the first monomer compound, the second monomer compound and the third monomer compound in chloroform, then adding them to a chloroform solution of anhydrous FeCl 3 under nitrogen protection, performing a polymerization reaction at 20-25° C. (e.g., 24-96 hours), then adding methanol to precipitate the polymerization product, and finally extracting the precipitate in ethanol (e.g., 24-96 hours); under a nitrogen environment, dissolving OH—(R 43 ) s —O—R 44 and diisocyanate OCN—R 42 —NCO in a solvent (e.g., N,N-dimethylformamide), stirring and reacting at 65-75° C.
  • a solvent e.g., N,N-dimethylformamide
  • the polythiophene conductive polymer includes a first structural unit, a second structural unit, a third structural unit and a fourth structural unit.
  • the method comprises the steps of: dissolving the first monomer compound, the precursor compound of the second monomer compound and the third monomer compound in chloroform, then adding them to an anhydrous FeCl 3 chloroform solution under nitrogen protection, performing a polymerization reaction at 20-25° C.
  • the polythiophene conductive polymer includes a first structural unit, a second structural unit, a third result
  • polythiophene conductive polymers with different molecular weights can be obtained.
  • the embodiment of the present application also provides a positive electrode slurry.
  • the positive electrode slurry includes a solvent and a non-solvent component.
  • the non-solvent component includes a positive electrode active material, a positive electrode binder and a positive electrode conductor.
  • the positive electrode conductor includes the polythiophene conductive polymer described above in the present application.
  • the polythiophene conductive polymer provided in the embodiments of the present application can be used in both non-aqueous positive electrode slurry and aqueous positive electrode slurry.
  • the solvent includes a non-aqueous solvent, which may optionally include N-methylpyrrolidone
  • the positive electrode binder includes an oily binder
  • n1/(n1+n2+n3+n4) may be 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, or a range consisting of any of the above values.
  • n1/(n1+n2+n3+n4) is within the above range, the dispersibility of the non-aqueous positive electrode slurry can be improved, the processing performance of the prepared positive electrode sheet can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an oily binder, and as an example, the positive electrode binder may include one or more of polyvinylidene fluoride, polyimide, and polyurethane.
  • the weight average molecular weight of polyvinylidene fluoride may be 50,000-2,000,000, thereby improving the bonding force of the positive electrode sheet and the processing performance of the positive electrode sheet.
  • the positive electrode binder includes an oily binder, 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.25, for example, n2/(n1+n2+n3+n4) can be 0, 0.05, 0.10, 0.15, 0.20, 0.25, or a range consisting of any of the above values.
  • the positive electrode binder includes an oily binder, 0.35 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.65, for example, (n3+n4)/(n1+n2+n3+n4) can be 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, or a range consisting of any of the above values.
  • n4/(n3+n4) can be 0, 0.05, 0.10, 0.12, 0.15, 0.20, or a range consisting of any of the above values.
  • n4/(n3+n4) is within the above range, the processing performance of the positive electrode sheet and the battery can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the solvent includes a non-aqueous solvent, which may optionally include N-methylpyrrolidone
  • the positive electrode binder includes an oily binder, and 0.35 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.65, 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.25, 0.35 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.65, and 0 ⁇ n4/(n3+n4) ⁇ 0.15.
  • the solvent includes a non-aqueous solvent, which may optionally include N-methylpyrrolidone
  • the positive electrode binder includes an oily binder, and 0.40 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.60, 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.10, 0.40 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60, and 0 ⁇ n4/(n3+n4) ⁇ 0.15.
  • the solvent includes a non-aqueous solvent, which may optionally include N-methylpyrrolidone
  • the solvent includes water
  • the positive electrode binder includes an aqueous binder
  • n1/(n1+n2+n3+n4) can be 0.05, 0.08, 0.11, 0.15, 0.20, 0.22, 0.25, or a range consisting of any of the above values.
  • n1/(n1+n2+n3+n4) is within the above range, the dispersibility of the aqueous positive electrode slurry can be improved, the adhesion and processing performance of the prepared positive electrode sheet can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder.
  • the positive electrode binder may include one or more of carboxymethyl cellulose and its derivatives, sodium alginate, polyacrylic acid and its derivatives, agarose, gelatin, carrageenan, xanthan gum, guar gum, polyvinyl alcohol, and polyacrylamide.
  • carboxymethyl cellulose and its derivatives sodium alginate
  • polyacrylic acid and its derivatives sodium alginate
  • agarose gelatin
  • carrageenan xanthan gum
  • guar gum polyvinyl alcohol
  • polyacrylamide polyacrylamide
  • the positive electrode binder includes an aqueous binder, 0.15 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.45, for example, n2/(n1+n2+n3+n4) can be 0.15, 0.20, 0.25, 0.30, 0.36, 0.40, 0.45, or a range consisting of any of the above values.
  • n2/(n1+n2+n3+n4) is within the above range, the heating efficiency of the positive electrode sheet can be improved, the bonding force and cohesion of the positive electrode sheet can be enhanced, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder, 0.30 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.80, for example, (n3+n4)/(n1+n2+n3+n4) can be 0.30, 0.35, 0.40, 0.42, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, or a range consisting of any of the above values.
  • the positive electrode binder includes an aqueous binder, 0 ⁇ n4/(n3+n4) ⁇ 0.20, for example, n4/(n3+n4) can be 0, 0.03, 0.04, 0.05, 0.08, 0.10, 0.12, 0.15, 0.20, or a range consisting of any of the above values.
  • n4/(n3+n4) is within the above range, the processing performance of the positive electrode sheet and the battery can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the solvent includes water
  • the positive electrode binder includes an aqueous binder
  • the solvent includes water
  • the positive electrode binder includes an aqueous binder, and 0.08 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.22, 0.25 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.40, 0.40 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60, and 0.04 ⁇ n4/(n3+n4) ⁇ 0.15.
  • the solvent includes water
  • the positive electrode binder includes an aqueous binder, and 0.11 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.22, 0.25 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.36, 0.42 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60, and 0.04 ⁇ n4/(n3+n4) ⁇ 0.15.
  • the positive electrode active material may include one or more of a lithium transition metal oxide, a lithium-containing phosphate, and their respective modified compounds.
  • lithium transition metal oxides may include lithium cobalt oxide, lithium nickel oxide, One or more of lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and their respective modified compounds.
  • lithium-containing phosphates may include lithium iron phosphate, a composite material of lithium iron phosphate and carbon, lithium manganese phosphate, a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, a composite material of lithium iron manganese phosphate and carbon, and their respective modified compounds.
  • the present application is not limited to these materials, and other conventionally known materials that can be used as battery positive electrode active materials may also be used.
  • the positive electrode active material may include a lithium-containing phosphate, optionally including one or more of lithium iron phosphate, lithium manganese phosphate, lithium manganese iron phosphate, and their respective modified compounds. These positive electrode active materials may be used alone or in combination of two or more.
  • the modified compounds of the above-mentioned positive electrode active materials may be the ones that undergo doping modification and/or surface coating modification on the positive electrode active materials.
  • the positive electrode slurry may further include a second conductive agent.
  • the second conductive agent may include one or more of superconducting carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the content of the polythiophene conductive polymer in the non-solvent component may be 0.2-4%, optionally 0.5-3%, based on the total weight of the non-solvent component.
  • the relative contents of different structural units in polythiophene conductive polymers can be measured by nuclear magnetic resonance spectroscopy (NMR).
  • the embodiment of the present application also provides a positive electrode plate.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector.
  • the positive electrode film layer includes a positive electrode active material, a positive electrode binder and a positive electrode conductor.
  • the positive electrode conductor includes the polythiophene conductive polymer described above in the present application.
  • the positive electrode current collector has two surfaces opposite to each other in the thickness direction thereof, and the positive electrode film layer is arranged on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • a metal foil aluminum foil may be used.
  • the aluminum foil may be 1060, 1070, 1100 or 1235, and the purity may be greater than 99%.
  • the composite current collector may include a polymer material base layer and a metal material layer formed on at least one surface of the polymer material base layer.
  • the metal material may include one or more of aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy.
  • the polymer material base layer may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS) and polyethylene (PE).
  • the thickness of the positive electrode current collector may be 10-20 ⁇ m.
  • the positive electrode binder includes an oily binder, and as an example, the positive electrode binder may include one or more of polyvinylidene fluoride, polyimide, and polyurethane.
  • the weight average molecular weight of polyvinylidene fluoride may be 50,000-2,000,000, thereby improving the bonding force of the positive electrode sheet and the processing performance of the positive electrode sheet.
  • the positive electrode binder includes an oily binder, and 0.35 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.65.
  • n1/(n1+n2+n3+n4) can be 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, or a range consisting of any of the above values.
  • n1/(n1+n2+n3+n4) is within the above range, the uniformity of the positive electrode film layer can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an oily binder, 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.25, for example, n2/(n1+n2+n3+n4) can be 0, 0.05, 0.10, 0.15, 0.20, 0.25, or a range consisting of any of the above values.
  • This can improve the uniformity of the positive electrode film layer and also improve the dynamic performance of the positive electrode sheet and the battery.
  • the positive electrode binder includes an oily binder, 0.35 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.65, for example, (n3+n4)/(n1+n2+n3+n4) can be 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, or a range consisting of any of the above values.
  • the positive electrode binder includes an oily binder, 0 ⁇ n4/(n3+n4) ⁇ 0.20, for example, n4/(n3+n4) can be 0, 0.05, 0.10, 0.12, 0.15, 0.20, or a range consisting of any of the above values.
  • n4/(n3+n4) is within the above range, the processing performance of the positive electrode sheet and the battery can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an oily binder, and 0.35 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.65, 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.25, 0.35 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.65, and 0 ⁇ n4/(n3+n4) ⁇ 0.15.
  • the positive electrode binder includes an oily binder, and 0.40 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.60, 0 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.10, 0.40 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60, and 0 ⁇ n4/(n3+n4) ⁇ 0.15.
  • the positive electrode binder includes an aqueous binder.
  • the positive electrode binder may include one or more of carboxymethyl cellulose and its derivatives, sodium alginate, polyacrylic acid and its derivatives, agarose, gelatin, carrageenan, xanthan gum, guar gum, polyvinyl alcohol, and polyacrylamide.
  • carboxymethyl cellulose and its derivatives sodium alginate
  • polyacrylic acid and its derivatives sodium alginate
  • agarose gelatin
  • carrageenan xanthan gum
  • guar gum polyvinyl alcohol
  • polyacrylamide polyacrylamide
  • the positive electrode binder includes an aqueous binder, and 0.05 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.25.
  • n1/(n1+n2+n3+n4) can be 0.05, 0.08, 0.11, 0.15, 0.20, 0.22, 0.25, or a range consisting of any of the above values.
  • n1/(n1+n2+n3+n4) is within the above range, the uniformity of the positive electrode film layer can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder, 0.15 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.45, for example, n2/(n1+n2+n3+n4) can be 0.15, 0.20, 0.25, 0.30, 0.36, 0.40, 0.45, or a range consisting of any of the above values.
  • n2/(n1+n2+n3+n4) is within the above range, the heating efficiency of the positive electrode sheet can be improved, the bonding force and cohesion of the positive electrode sheet can be enhanced, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder, 0.30 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.80, for example, (n3+n4)/(n1+n2+n3+n4) can be 0.30, 0.35, 0.40, 0.42, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, or a range consisting of any of the above values.
  • the positive electrode binder includes an aqueous binder, 0 ⁇ n4/(n3+n4) ⁇ 0.20, for example, n4/(n3+n4) can be 0, 0.03, 0.04, 0.05, 0.08, 0.10, 0.12, 0.15, 0.20, or a range consisting of any of the above values.
  • n4/(n3+n4) is within the above range, the processing performance of the positive electrode sheet and the battery can be improved, and the dynamic performance of the positive electrode sheet and the battery can also be improved.
  • the positive electrode binder includes an aqueous binder, and 0.05 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.25, 0.15 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.45, 0.30 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.80, and 0.04 ⁇ n4/(n3+n4) ⁇ 0.15.
  • the positive electrode binder includes an aqueous binder, and 0.08 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.22, 0.25 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.40, 0.40 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60, and 0.04 ⁇ n4/(n3+n4) ⁇ 0.15.
  • the positive electrode binder includes an aqueous binder, and 0.11 ⁇ n1/(n1+n2+n3+n4) ⁇ 0.22, 0.25 ⁇ n2/(n1+n2+n3+n4) ⁇ 0.36, 0.42 ⁇ (n3+n4)/(n1+n2+n3+n4) ⁇ 0.60, and 0.04 ⁇ n4/(n3+n4) ⁇ 0.15.
  • the positive electrode conductive agent may further include a second conductive agent.
  • the second conductive agent may include one or more of superconducting carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the content of the polythiophene conductive polymer in the positive electrode film layer may be 0.2-4%, optionally 0.5-3%, based on the total weight of the positive electrode film layer.
  • the content of the positive electrode conductive agent (including the polythiophene conductive polymer and the second conductive agent) in the positive electrode film layer may be 0.5-4%, based on the total weight of the positive electrode film layer.
  • the content of the positive electrode active material in the positive electrode film layer may be 92-98%, based on the total weight of the positive electrode film layer.
  • the content of the positive electrode binder in the positive electrode film layer may be 1-10%, based on the total weight of the positive electrode film layer.
  • the positive electrode active material may be a material known in the art, and the present application embodiment does not limit this.
  • the positive electrode active material includes a material that can reversibly extract and insert lithium ions.
  • the positive electrode active material may include one or more of a lithium transition metal oxide, a lithium-containing phosphate, and their respective modified compounds.
  • lithium transition metal oxides may include lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, Lithium nickel cobalt aluminum oxide, and one or more of their respective modified compounds.
  • lithium-containing phosphates may include lithium iron phosphate, a composite material of lithium iron phosphate and carbon, lithium manganese phosphate, a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, a composite material of lithium iron manganese phosphate and carbon, and one or more of their respective modified compounds.
  • the present application is not limited to these materials, and other conventionally known materials that can be used as battery positive electrode active materials may also be used.
  • the positive electrode active material may include a lithium-containing phosphate, optionally including one or more of lithium iron phosphate, lithium manganese phosphate, lithium manganese iron phosphate, and their respective modified compounds. These positive electrode active materials may be used alone or in combination of two or more.
  • the modified compounds of the above-mentioned positive electrode active materials may be the ones that undergo doping modification and/or surface coating modification on the positive electrode active materials.
  • the positive electrode active material may include a lithium-containing phosphate, and the volume distribution particle size Dv50 of the positive electrode active material may be 1-10 ⁇ m.
  • the positive electrode active material may include lithium-containing phosphate, and the surface density of the positive electrode sheet may be 0.2-0.8 g/1540.25 mm 2 .
  • the positive electrode active material may include lithium-containing phosphate, and the compaction density of the positive electrode sheet may be 2.2-2.5 g/cm 3 , thereby enabling the battery to have a high energy density.
  • the embodiment of the present application also provides a method for preparing a positive electrode plate.
  • the method comprises the following steps: coating the positive electrode slurry as described above on at least one surface of the positive electrode current collector, drying and rolling to obtain an initial positive electrode sheet; irradiating the initial positive electrode sheet obtained with a laser, and obtaining a positive electrode sheet after completion.
  • the laser wavelength may be 445-505 nm.
  • the positive electrode active material in the positive electrode plate has a low absorption rate for blue light (wavelength of 445-505nm), while the polythiophene conductive polymer provided in the embodiment of the present application has a high blue light absorption capacity. Therefore, by using the polythiophene conductive polymer provided in the embodiment of the present application in the positive electrode plate and irradiating the positive electrode plate with blue light, rapid photothermal conversion can be performed, the heating efficiency can be improved, and the adverse effects of blue light irradiation on the positive electrode active material can be reduced.
  • the polythiophene conductive polymer can be quickly heated, thereby releasing some stress, which is conducive to forming a positive electrode film layer with higher porosity, thereby reducing the amount of residual solvent and improving the electrolyte wettability of the positive electrode plate.
  • Blue light irradiation can also remove substances such as dispersants and surfactants introduced during the processing of the positive electrode plate.
  • the heating efficiency is high, and the heating temperature is usually higher than the softening point of the positive electrode binder, thereby allowing the positive electrode binder to be evenly distributed in the thickness direction of the positive electrode plate, thereby helping to improve the cohesion and adhesion of the positive electrode plate, reduce the positive electrode resistance, and thus improve the rate performance of the battery.
  • the laser may be emitted continuously.
  • the number of lasers may be 1-10, and the total power may be 100-2500W.
  • the time for the initial positive electrode plate to pass through the laser spot can be 0.05-0.5s.
  • the time for the initial positive electrode plate to pass through the laser spot refers to the time from the initial positive electrode plate contacting the laser spot to the laser spot leaving the laser spot and stopping irradiation.
  • the vertical distance between the laser and the initial positive electrode plate can be 5-15 cm.
  • the battery cell includes a negative electrode plate.
  • the structure and composition of the negative electrode plate can be selected according to the type of the battery cell, and the embodiment of the present application is not limited to this.
  • the negative electrode sheet may include a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector, wherein the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two surfaces opposite to each other in the thickness direction thereof, and the negative electrode film layer is arranged on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • metal foils copper foil, copper alloy foil, aluminum foil, and aluminum alloy foil may be used.
  • the composite current collector may include a polymer material base layer and a metal material layer formed on at least one surface of the polymer material base layer.
  • the metal material may include one or more of copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy.
  • the polymer material base layer may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE).
  • the negative electrode active material may adopt materials known in the art.
  • the negative electrode active material may include, but is not limited to, one or more of natural graphite, artificial graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, and lithium titanate.
  • Silicon-based materials may include one or more of elemental silicon, silicon oxide, silicon-carbon composite, silicon-nitrogen composite, and silicon alloy materials.
  • Tin-based materials may include one or more of elemental tin, tin oxide, and tin alloy materials. The present application is not limited to these materials, and other conventionally known materials that can be used as negative electrode active materials may also be used. These negative electrode active materials may be used alone or in combination of two or more.
  • the negative electrode film layer may further include a negative electrode conductive agent.
  • a negative electrode conductive agent may include one or more of superconducting carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the negative electrode film layer may further include a negative electrode binder.
  • the negative electrode binder may include styrene-butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, water-based acrylic resin (e.g., polyacrylic acid PAA, polymethacrylic acid PMAA, sodium polyacrylate PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA) and carboxymethyl chitosan (CMCS).
  • SBR styrene-butadiene rubber
  • SR-1B water-soluble unsaturated resin
  • PAM polyacrylamide
  • PVA polyvinyl alcohol
  • SA sodium alginate
  • CMCS carboxymethyl chitosan
  • the negative electrode film layer may further include other additives.
  • the other additives may include a thickener, such as sodium carboxymethyl cellulose (CMC), a PTC thermistor material, and the like.
  • the negative electrode film layer is usually formed by coating the negative electrode slurry on the negative electrode current collector, drying and cold pressing.
  • the negative electrode slurry is usually formed by dispersing the negative electrode active material, the optional negative electrode conductive agent, the optional negative electrode binder, and other optional additives in a solvent and stirring them uniformly.
  • the solvent can be N-methylpyrrolidone (NMP) or deionized water, but is not limited thereto.
  • the negative electrode plate does not exclude other additional functional layers besides the negative electrode film layer.
  • the negative electrode plate may also include a conductive primer layer (e.g., composed of a conductive agent and a binder) sandwiched between the negative electrode current collector and the negative electrode film layer and disposed on the surface of the negative electrode current collector; in some embodiments, the negative electrode plate may also include a protective layer covering the surface of the negative electrode film layer.
  • the negative electrode plate may include a negative electrode current collector and a first metal layer disposed on at least one surface of the negative electrode current collector, and the metal element in the first metal layer may include lithium element.
  • the metal material in the first metal layer may include one or more of lithium element and lithium alloy.
  • Lithium alloys may be alloys of metallic lithium and other metallic elements or non-metallic elements.
  • other metallic elements in lithium alloys may include one or more of tin, zinc, aluminum, magnesium, silver, gold, gallium, indium, and platinum.
  • the non-metallic elements in the lithium alloy may include one or more elements of boron, carbon, and silicon.
  • the negative electrode sheet may include a negative electrode current collector but not include the first metal layer, so as to be assembled into a negative electrode metal-free battery cell.
  • the negative electrode plate may also be made of a sheet (or foil) of lithium or a lithium alloy.
  • the battery cell provided in the embodiment of the present application includes an electrolyte.
  • the electrolyte plays a role of conducting ions between the positive electrode plate and the negative electrode plate.
  • the present application does not specifically limit the type of electrolyte, which can be selected according to needs.
  • the electrolyte may include one or more of a solid electrolyte, a gel electrolyte, and a liquid electrolyte (i.e., an electrolyte).
  • the electrolyte is an electrolyte solution, which includes an electrolyte salt and a solvent.
  • the electrolyte salt may include one or more of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium bisfluorosulfonyl imide (LiFSI), lithium bistrifluoromethanesulfonyl imide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluorooxalatoborate (LiDFOB), lithium dioxalatoborate (LiBOB), lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorobisoxalatophosphate (LiDFOP) and lithium tetrafluorooxalatophosphate (LiPF 6 ), lithium tetrafluoroxalatophosphate (LiDFOP) and lithium te
  • the solvent may include one or more of an ester solvent, a sulfone solvent, and an ether solvent.
  • the solvent may include, but is not limited to, ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), butylene carbonate (BC), fluoroethylene carbonate (FEC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB) , ethyl butyrate (EB), 1,4-butyrol
  • the electrolyte may further include additives.
  • the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high temperature performance, and additives that improve battery low temperature power performance.
  • the battery cell provided in the embodiment of the present application may also include a separator.
  • the separator may be disposed between the positive electrode plate and the negative electrode plate, and mainly serves to prevent internal short circuits.
  • the present application has no particular restrictions on the type of separator, and any known porous structure membrane with good chemical stability and mechanical stability may be selected.
  • the material of the isolation membrane may include one or more of glass fiber, non-woven fabric, polyethylene, polypropylene, polyvinylidene fluoride, and polyimide.
  • the isolation membrane may be a single-layer film or a multi-layer composite film. When the isolation membrane is a multi-layer composite film, the materials of each layer are the same or different.
  • the positive electrode sheet, the separator, the negative electrode sheet and the electrolyte can be assembled to form a battery cell.
  • the positive electrode sheet, the separator, the negative electrode sheet and the electrolyte can be assembled to form a battery cell.
  • the negative electrode sheet is wound and/or laminated to form an electrode assembly, which is placed in an outer package, dried and injected with the above-mentioned electrolyte, and then vacuum packaged, left to stand, formed, and shaped to obtain a battery cell.
  • Multiple battery cells can be further connected in series, in parallel, or in a mixed connection to form a battery module.
  • Multiple battery modules can also be connected in series, in parallel, or in a mixed connection to form a battery pack.
  • multiple battery cells can also directly form a battery pack.
  • the present application also provides an electrical device, which includes a battery provided in the present application.
  • the battery can be used as a power source for the electrical device, or as an energy storage unit for the electrical device.
  • the electrical device can be, but is not limited to, a mobile device (such as a mobile phone, a tablet computer, a laptop computer, etc.), an electric vehicle (such as a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship and a satellite, an energy storage system, etc.
  • the electrical device can select a specific type of battery according to its usage requirements, for example, a battery cell, a battery module or a battery pack.
  • Fig. 6 is a schematic diagram of an electric device as an example.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
  • a battery pack or a battery module may be used.
  • the electric device may be a mobile phone, a tablet computer, a notebook computer, etc.
  • the electric device is usually required to be light and thin, and a battery cell may be used as a power source.
  • 3-pentyloxythiophene (the first monomer compound) and 3-thiophene methanol (the third monomer compound) were dry mixed at a molar ratio of 3:4, and about 10 g was dissolved in 100 mL of chloroform. Then, 500 mL of anhydrous FeCl 3 chloroform solution with a concentration of 0.2 mol/L was added in a nitrogen environment, and the polymerization reaction was carried out at 25° C. for about 24 hours. Then, methanol was added to the reaction system to precipitate the polymerization product, and the obtained precipitate was extracted in ethanol for 48 hours, and the intermediate was obtained after drying.
  • the polythiophene conductive polymer includes the first structural unit, the third structural unit and the fourth structural unit shown in Table 1, and n1:n2:(n3+n4) is 3:0:4, and n4/(n3+n4) is 0.12.
  • the number average molecular weight of the polythiophene conductive polymer is shown in Table 1.
  • the relative content of different structural units in the polythiophene conductive polymer can be obtained by nuclear magnetic resonance spectroscopy (NMR).
  • the positive electrode active material lithium iron phosphate with a volume distribution particle size Dv50 of 7 ⁇ m is mixed with polyvinylidene fluoride and polythiophene conductive polymer.
  • the compound and conductive carbon black (Super P) were added into NMP in a weight ratio of 96:2:1.5:0.5 and uniformly dispersed to obtain a positive electrode slurry; the positive electrode slurry was coated on both sides of a 13 ⁇ m thick 1060 aluminum foil, then dried to evaporate the solvent, and then cold pressed to obtain an initial positive electrode sheet with a surface density of 0.6 g/1540.25 mm2 and a compaction density of 2.5 g/ cm3 .
  • One of the positive electrode film layers of the above-mentioned initial positive electrode sheet is continuously irradiated with 495nm blue light composed of 5 lasers with a total power of 2000W for a residence time of 0.5s, and the vertical distance between the laser and the initial positive electrode sheet is 10cm; then the other positive electrode film layer of the initial positive electrode sheet is treated in the same way, and a positive electrode sheet is obtained after completion.
  • the negative electrode active material artificial graphite, conductive agent conductive carbon black (Super P), thickener carboxymethyl cellulose, and binder styrene butadiene rubber (SBR) are fully stirred and mixed in a proper amount of solvent deionized water at a weight ratio of 96:1:1:2 to form a uniform negative electrode slurry; the negative electrode slurry is coated on both sides of a 6 ⁇ m thick copper foil, and after drying and cold pressing, a negative electrode sheet is obtained.
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) are mixed in a volume ratio of 1:1:1 to obtain an organic solvent, and then fully dried LiPF 6 is dissolved in the above organic solvent to prepare an electrolyte with a concentration of 1 mol/L.
  • a porous polyethylene membrane was used as the separator.
  • the positive electrode sheet, the separator, and the negative electrode sheet are stacked and wound in order to obtain an electrode assembly; the electrode assembly is placed in an outer package, and after drying, the electrolyte is injected, and the battery is obtained after vacuum packaging, standing, formation and other processes.
  • the preparation method of the battery is similar to that of Example 1-1, except that the preparation processes of the polythiophene conductive polymer and the positive electrode are different.
  • 3-Butoxythiophene (the first monomer compound) and 3-thiophene methanol (the third monomer compound) were dry mixed at a molar ratio of 3:4, and about 10 g was dissolved in 100 mL of chloroform. Then, 500 mL of 0.2 mol/L anhydrous FeCl 3 chloroform solution was added in a nitrogen environment, and the polymerization reaction was carried out at 25°C for about 48 hours. Then, methanol was added to the reaction system to precipitate the polymerization product, and the obtained precipitate was extracted in ethanol for 36 hours, and the intermediate was obtained after drying.
  • the polythiophene conductive polymer includes the first structural unit, the third structural unit and the fourth structural unit shown in Table 1, and n1:n2:(n3+n4) is 3:0:4, and n4/(n3+n4) is 0.12.
  • the number average molecular weight of the polythiophene conductive polymer is shown in Table 1.
  • the positive electrode active material lithium iron phosphate with a volume distribution particle size Dv50 of 5 ⁇ m, polyvinylidene fluoride, polythiophene conductive polymer, and conductive carbon black (Super P) were added to NMP in a weight ratio of 97:1:1.3:0.7 and uniformly dispersed to obtain a positive electrode slurry.
  • the positive electrode slurry was coated on both sides of a 15 ⁇ m thick 1070 aluminum foil, and then dried to evaporate the solvent, and then cold pressed to obtain an initial positive electrode sheet with a surface density of 0.65 g/1540.25 mm 2 and a compaction density of 2.45 g/cm 3 .
  • One of the positive electrode film layers of the above-mentioned initial positive electrode sheet is continuously irradiated with 455nm blue light with a total power of 2500w composed of 4 lasers with a residence time of 0.3s, and the vertical distance between the laser and the initial positive electrode sheet is 5cm; then the other positive electrode film layer of the initial positive electrode sheet is treated in the same way, and a positive electrode sheet is obtained after completion.
  • the preparation method of the battery is similar to that of Example 1-1, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • the polythiophene conductive polymer includes the first structural unit, the third structural unit and the fourth structural unit shown in Table 1, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are shown in Table 1.
  • the preparation method of the battery is similar to that of Example 1-1, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • hexamethylene diisocyanate is used instead of diphenylmethane diisocyanate.
  • the polythiophene conductive polymer includes the first structural unit, the third structural unit and the fourth structural unit shown in Table 1, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are as shown in Table 1.
  • the preparation method of the battery is similar to that of Example 1-1, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • dicyclohexylmethane diisocyanate is used instead of diphenylmethane diisocyanate.
  • the polythiophene conductive polymer includes the first structural unit, the third structural unit and the fourth structural unit shown in Table 1, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are respectively shown in Table 1.
  • the preparation method of the battery is similar to that of Example 1-1, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • the prepared polythiophene conductive polymer includes the first structural unit and the third structural unit shown in Table 1, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are shown in Table 1.
  • the preparation method of the battery is similar to that of Example 1-1, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • 3-pentyloxythiophene (the first monomer compound), methyl 2-(thiophene-3-oxy) propionate (the precursor compound of the second monomer compound), and 3-thiophene methanol (the third monomer compound) were dry mixed at a molar ratio of 5:0.5:4.5, and a total of about 10 g of the solution was taken.
  • the polythiophene conductive polymer includes the first structural unit, the second structural unit and the third structural unit shown in Table 1, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are as shown in Table 1.
  • the preparation method of the battery is similar to that of Example 1-1, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • 3-pentyloxythiophene (the first monomer compound), methyl 2-(thiophene-3-oxy)propionate (the precursor compound of the second monomer compound), and 3-thiophene methanol (the third monomer compound) were dry mixed at a molar ratio of 5:1:4.5, and about 10 g was dissolved in 100 mL of chloroform.
  • the polythiophene conductive polymer includes the first structural unit, the second structural unit, the third structural unit and the fourth structural unit shown in Table 1, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are as shown in Table 1.
  • the preparation method of the battery is similar to that of Example 1-1, except that the number average molecular weight of the polythiophene conductive polymer is different, as shown in Table 3 for details.
  • the preparation method of the battery is similar to that of Example 1-1, except that the content and number average molecular weight of each structural unit in the polythiophene conductive polymer are different, as shown in Table 3 for details.
  • the preparation method of the battery is similar to that of Example 1-1, except that the content and number average molecular weight of each structural unit in the polythiophene conductive polymer are different, as shown in Table 3 for details.
  • one or more of the parameters such as the type and concentration of the monomer, the concentration of the oxidant FeCl 3 , the reaction temperature and the reaction time can be adjusted according to methods known in the art to obtain different number average molecular weights.
  • the preparation method of the battery is similar to that of Example 1-1, except that the preparation process of the positive electrode plate is different.
  • the positive electrode active material lithium iron phosphate with a volume distribution particle size Dv50 of 7 ⁇ m is mixed with polyvinylidene fluoride and conductive carbon black.
  • Super P was added to NMP at a weight ratio of 96:2:2 and uniformly dispersed to obtain a positive electrode slurry; the positive electrode slurry was coated on both sides of a 13 ⁇ m thick 1060 aluminum foil, then dried to evaporate the solvent, and then cold pressed to obtain a positive electrode sheet with a surface density of 0.6 g/1540.25 mm2 and a compaction density of 2.5 g/ cm3 .
  • the preparation method of the battery is similar to that of Example 1-1, except that the preparation process of the positive electrode plate is different.
  • the positive electrode active material lithium iron phosphate with a volume distribution particle size Dv50 of 7 ⁇ m, polyvinylidene fluoride, homopolymer polythiophene (the monomer is thiophene, and the number average molecular weight is between 15000-20000), and conductive carbon black (Super P) are added into NMP at a weight ratio of 96:2:1.3:0.7 and uniformly dispersed to obtain a positive electrode slurry; the positive electrode slurry is coated on both sides of a 13 ⁇ m thick 1060 aluminum foil, then dried to evaporate the solvent, and then cold pressed to obtain an initial positive electrode sheet with a surface density of 0.6 g/1540.25 mm2 and a compaction density of 2.5 g/ cm3 .
  • One of the positive electrode film layers of the above-mentioned initial positive electrode sheet is continuously irradiated with 495nm blue light composed of 5 lasers with a total power of 2000W for a residence time of 0.5s, and the vertical distance between the laser and the initial positive electrode sheet is 10cm; then the other positive electrode film layer of the initial positive electrode sheet is treated in the same way, and a positive electrode sheet is obtained after completion.
  • the resistance tester can be Yuanneng Technology BER2500.
  • the test temperature is 25°C.
  • the positive electrode sheet was washed with N-methylpyrrolidone to remove the positive electrode film layer on one side and dried, and then the single-sided coated positive electrode sheet was cut into 20mm ⁇ 100mm test samples for use; the test sample was adhered to the side to be tested with double-sided tape, and compacted with a pressure roller to make the double-sided tape and the test sample completely fit; the other side of the double-sided tape was adhered to the stainless steel surface, and one end of the test sample was bent in the opposite direction with a bending angle of 180°; a high-speed rail tensile testing machine was used for testing, one end of the stainless steel was fixed to the lower fixture of the tensile testing machine, the bent end of the test sample was fixed to the upper fixture, the angle of the test sample was adjusted to ensure that the upper and lower ends were in a vertical position, and then the test sample was stretched at a speed of 50mm/min until the test sample was completely peeled off from the substrate, the displacement and force in the process were recorded, and the force when
  • the positive electrode plate was washed with N-methylpyrrolidone to remove the positive electrode film layer on one side and dried, and then punched into a single-sided circular plate with a diameter of 14 mm and weighed; at the same time, the weight of the corresponding positive electrode current collector under the 14 mm diameter round plate was weighed to obtain the weight of the positive electrode film layer, and then the mass of the positive electrode active material was calculated.
  • a 2032 button battery was assembled with a 2032 button battery negative electrode shell, nickel foam, a 16 mm diameter lithium sheet, a 18 mm diameter Celgard2325 separator, 0.1 g 1 mol ⁇ L -1 LiPF 6 EC:DMC:EMC (mass ratio 1:1:1) electrolyte, a 14 mm diameter single-sided circular electrode piece, and a 2032 button battery positive electrode shell.
  • the assembled button cell was left to rest for 12 hours before testing.
  • the mass of the positive electrode active material multiplied by the theoretical gram capacity is is the battery capacity, denoted as C.
  • the button cell is charged to the upper cut-off voltage at a current of 0.1C, and then discharged to the upper cut-off voltage at a current of 0.1C.
  • the gram capacity of the positive electrode active material is obtained by dividing the discharge capacity of the button cell by the mass of the positive electrode active material.
  • the batteries prepared in the examples and comparative examples were charged to a full charge state (100% SOC) at a constant current of 0.33C, and then discharged to 0.5Cn (Cn represents the battery capacity) at a constant current of 0.33C to adjust the battery to 50% SOC; the battery was left to stand for 30 minutes, and the voltage after the end of the standing was recorded as V1; then the battery was discharged at a current of 3C (recorded as I) for 30 seconds, and the discharge cut-off voltage was recorded as V2.
  • the DC internal resistance DCR of the battery (V1-V2)/I, V1 represents the end-of-standing voltage, V2 represents the discharge cut-off voltage, and I represents the discharge current.
  • the batteries prepared in each embodiment and comparative example were charged to 3.65V at a constant current of 0.33C, and then continued to be charged at a constant voltage to a current of 0.05C.
  • the battery was discharged to 2.5V at a constant current of 0.33C to obtain the discharge capacity of the battery at a rate of 0.33C; after the battery was stood for 30 minutes, it was charged to 3.65V at a constant current of 0.33C, and then charged to a current of 0.05C at a constant voltage.
  • the battery was discharged to 2.5V at a constant current of 3C to obtain the discharge capacity of the battery at a rate of 3C.
  • the rate performance of the battery is represented by the ratio of the discharge capacity of the battery at a rate of 3C to the discharge capacity of the battery at a rate of 0.33C. The larger the ratio, the better the rate performance of the battery.
  • the positive electrode sheet provided in the embodiments of the present application has the characteristics of low resistance, high adhesion, high porosity, and high gram capacity after being irradiated with blue light. When applied to batteries, it can reduce the internal resistance of the battery and improve the rate performance of the battery.
  • Figure 7 is the discharge curves of the batteries of Example 1-1 and Comparative Example 1-1 at different rates. As can be seen from Figure 7, the battery prepared in Example 1-1 has a higher discharge capacity retention rate at a 3C rate.
  • the positive electrode conductive agent in the positive electrode plates of Examples 1-1 to 1-21 includes a functionalized polythiophene conductive polymer, which has a higher absorption rate for blue light wavelengths and a higher heating efficiency when irradiated with blue light, thereby better improving the distribution of the positive electrode binder in the positive electrode plate, thereby enhancing the bonding force and cohesion of the positive electrode plate, and also reducing the positive electrode resistance; stress can also be released during the blue light irradiation process, which is conducive to the formation of a positive electrode film layer with a higher porosity, thereby improving the electrolyte wettability of the positive electrode plate.
  • the preparation method of the battery is similar to that of Example 1-1, except that the preparation processes of the polythiophene conductive polymer and the positive electrode are different.
  • 3-pentyloxythiophene (the first monomer compound), ethyl thiophene-3-oxyacetate (the precursor compound of the second monomer compound), and 3-thiophene methanol (the third monomer compound) were dry mixed at a molar ratio of 15:20:45, and about 10 g was dissolved in 100 mL of chloroform. Then, 500 mL of anhydrous FeCl 3 chloroform solution with a concentration of 0.2 mol/L was added in a nitrogen environment, and the polymerization reaction was carried out at 25° C. for about 48 hours; then, methanol was added to the reaction system to precipitate the polymerization product, and the obtained precipitate was extracted in ethanol for 36 hours, and the first intermediate was obtained after drying.
  • the polythiophene conductive polymer includes the first structural unit, the second structural unit, the third structural unit and the fourth structural unit shown in Table 4, and n1:n2:(n3+n4) is 15:20:45, and n4/(n3+n4) is 0.05.
  • the number average molecular weight of the polythiophene conductive polymer is shown in Table 4.
  • the positive electrode active material lithium iron phosphate with a volume distribution particle size Dv50 of 7 ⁇ m, sodium carboxymethyl cellulose, polythiophene conductive polymer, and conductive carbon black (Super P) were uniformly dispersed in deionized water in a weight ratio of 96:2:1.3:0.7 to obtain a positive electrode slurry; the positive electrode slurry was coated on both sides of a 20 ⁇ m thick 1070 aluminum foil, then dried to evaporate the solvent, and then cold pressed to obtain an initial positive electrode sheet with a surface density of 0.7 g/1540.25 mm2 and a compaction density of 2.4 g/ cm3 .
  • One of the positive electrode film layers of the above-mentioned initial positive electrode sheet is continuously irradiated with 485nm blue light with a total power of 2500w composed of 10 lasers with a residence time of 0.25s, and the vertical distance between the laser and the initial positive electrode sheet is 15cm; then the other positive electrode film layer of the initial positive electrode sheet is treated in the same way, and a positive electrode sheet is obtained after completion.
  • the preparation method of the battery is similar to that of Example 2-1, except that the preparation processes of the polythiophene conductive polymer and the positive electrode are different.
  • 3-pentyloxythiophene (the first monomer compound), methyl 2-(thiophene-3-oxy)propionate (the precursor compound of the second monomer compound), and 3-thiophene methanol (the third monomer compound) were dry mixed at a molar ratio of 15:20:45, and about 10 g was dissolved in 100 mL of chloroform. Then, 500 mL of anhydrous FeCl 3 chloroform solution with a concentration of 0.2 mol/L was added in a nitrogen environment, and the polymerization reaction was carried out at 25° C. for about 24 hours; then, methanol was added to the reaction system to precipitate the polymerization product, and the obtained precipitate was extracted in ethanol for 48 hours, and the first intermediate was obtained after drying.
  • the polythiophene conductive polymer includes the first structural unit, the second structural unit, the third structural unit and the fourth structural unit shown in Table 4, and n1:n2:(n3+n4) is 15:20:45, and n4/(n3+n4) is 0.05.
  • the number average molecular weight of the polythiophene conductive polymer is shown in Table 4.
  • the positive electrode active material lithium iron phosphate with a volume distribution particle size Dv50 of 5 ⁇ m, sodium alginate, polythiophene conductive polymer, and conductive carbon black (Super P) are added to deionized water in a weight ratio of 96.5:1.5:1.4:0.6 and uniformly dispersed to obtain a positive electrode slurry; the positive electrode slurry is coated on both sides of a 20 ⁇ m thick 1070 aluminum foil, then dried to evaporate the solvent, and then cold pressed to obtain an initial positive electrode sheet with a surface density of 0.7 g/1540.25 mm2 and a compaction density of 2.4 g/ cm3 .
  • One of the positive electrode film layers of the above-mentioned initial positive electrode sheet is continuously irradiated with 505nm blue light composed of 8 lasers with a total power of 1500w for a residence time of 0.2s, and the vertical distance between the laser and the initial positive electrode sheet is 7.5cm; then the other positive electrode film layer of the initial positive electrode sheet is treated in the same way, and a positive electrode sheet is obtained after completion.
  • the preparation method of the battery is similar to that of Example 2-2, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • the polythiophene conductive polymer includes the first structural unit, the second structural unit, the third structural unit and the fourth structural unit shown in Table 4, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are shown in Table 4.
  • the preparation method of the battery is similar to that of Example 2-2, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • the polythiophene conductive polymer includes the first structural unit, the second structural unit, the third structural unit and the fourth structural unit shown in Table 4, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are shown in Table 4.
  • the preparation method of the battery is similar to that of Example 2-2, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • the polythiophene conductive polymer includes the first structural unit, the second structural unit, the third structural unit and the fourth structural unit shown in Table 4, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are shown in Table 4.
  • the preparation method of the battery is similar to that of Example 2-2, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • the polythiophene conductive polymer includes the first structural unit, the second structural unit, the third structural unit and the fourth structural unit shown in Table 4, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are shown in Table 4.
  • the preparation method of the battery is similar to that of Example 2-2, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • the prepared polythiophene conductive polymer includes the first structural unit and the third structural unit shown in Table 4, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are shown in Table 4.
  • the preparation method of the battery is similar to that of Example 2-2, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • the prepared polythiophene conductive polymer includes the first structural unit, the third structural unit and the fourth structural unit shown in Table 4, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are shown in Table 4.
  • the preparation method of the battery is similar to that of Example 2-2, except that the structure and preparation process of the polythiophene conductive polymer are different.
  • the prepared polythiophene conductive polymer includes the first structural unit, the third structural unit and the fourth structural unit shown in Table 4, and the content of each structural unit and the number average molecular weight of the polythiophene conductive polymer are shown in Table 4.
  • the preparation method of the battery is similar to that of Example 2-2, except that the number average molecular weight of the polythiophene conductive polymer is different, as shown in Table 6 for details.
  • the preparation method of the battery is similar to that of Example 2-2, except that the content and number average molecular weight of each structural unit in the polythiophene conductive polymer are different, as shown in Table 6 for details.
  • the preparation method of the battery is similar to that of Example 2-2, except that the content and number average molecular weight of each structural unit in the polythiophene conductive polymer are different, as shown in Table 6 for details.
  • the preparation method of the battery is similar to that of Example 2-2, except that the pH of the second intermediate is adjusted to 7.5 with NaOH.
  • one or more of the parameters such as the type and concentration of the monomer, the concentration of the oxidant FeCl 3 , the reaction temperature and the reaction time can be adjusted according to methods known in the art to obtain different number average molecular weights.
  • the preparation method of the battery is similar to that of Example 2-2, except that the preparation process of the positive electrode plate is different.
  • the positive electrode active material lithium iron phosphate with a volume distribution particle size Dv50 of 5 ⁇ m, sodium alginate, and conductive carbon black (Super P) were uniformly dispersed in deionized water at a weight ratio of 96.5:1.5:2 to obtain a positive electrode slurry; the positive electrode slurry was coated on both sides of a 20 ⁇ m thick 1070 aluminum foil, and then dried to evaporate the solvent, and then cold pressed to obtain a surface density of 0.7g/1540.25mm 2 , positive electrode sheet with compaction density of 2.4g/cm 3 .
  • the preparation method of the battery is similar to that of Example 2-2, except that the preparation process of the positive electrode plate is different.
  • the positive electrode active material lithium iron phosphate with a volume distribution particle size Dv50 of 5 ⁇ m, sodium alginate, homopolymerized polythiophene (the monomer is thiophene, and the number average molecular weight is between 15000-20000), and conductive carbon black (Super P) are added into deionized water at a weight ratio of 96.5:1.5:1.4:0.6 and uniformly dispersed to obtain a positive electrode slurry; the positive electrode slurry is coated on both sides of a 20 ⁇ m thick 1070 aluminum foil, then dried to evaporate the solvent, and then cold pressed to obtain an initial positive electrode sheet with a surface density of 0.7 g/1540.25 mm2 and a compaction density of 2.4 g/ cm3 .
  • One of the positive electrode film layers of the above-mentioned initial positive electrode sheet is continuously irradiated with 505nm blue light composed of 8 lasers with a total power of 1500w for a residence time of 0.2s, and the vertical distance between the laser and the initial positive electrode sheet is 7.5cm; then the other positive electrode film layer of the initial positive electrode sheet is treated in the same way, and a positive electrode sheet is obtained after completion.
  • the positive electrode plate provided in the embodiments of the present application has the characteristics of low resistance, high adhesion, high porosity and high gram capacity after being irradiated with blue light. When applied to batteries, it can reduce the internal resistance of the battery and improve the rate performance of the battery.
  • the positive electrode conductive agent in the positive electrode sheets of Examples 2-1 to 2-23 includes functionalized polythiophene conductive polymers, which have a higher absorption rate for blue light wavelengths and a higher heating efficiency when irradiated with blue light. This can better improve the distribution of the positive electrode binder in the positive electrode sheet, thereby enhancing the bonding and cohesive forces of the positive electrode sheet and reducing the positive electrode resistance. Stress can also be released during blue light irradiation, which is conducive to forming a positive electrode film layer with a higher porosity, thereby improving the electrolyte wettability of the positive electrode sheet.

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Abstract

本申请公开了一种聚噻吩导电聚合物、正极浆料、正极极片及其制备方法、电池单体、电池和用电装置，聚噻吩导电聚合物包括式(1)所示的第一结构单元以及式(2)所示的第二结构单元、式(3)所示的第三结构单元和式(4)所示的第四结构单元中的至少一者。

Description

聚噻吩导电聚合物、正极浆料、正极极片及其制备方法、电池单体、电池和用电装置
相关申请的交叉引用
本申请要求享有于2023年07月03日提交的名称为“聚噻吩导电聚合物、正极浆料、正极极片及其制备方法、电池单体、电池和用电装置”的中国专利申请202310806166.1的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本申请涉及一种聚噻吩导电聚合物、正极浆料、正极极片及其制备方法、电池单体、电池和用电装置。
背景技术
近年来，电池被广泛应用于水力、火力、风力和太阳能电站等储能电源系统，以及电动工具、电动自行车、电动摩托车、电动汽车、军事装备、航空航天等多个领域。近年来，随着电池应用领域的不断拓展，对电池综合性能的要求也不断增加。但是，如何使电池兼具高能量密度以及良好的加工性能和倍率性能，仍是目前需要解决的技术难题。上述的陈述仅用于提供与本申请有关的背景技术信息，而不必然地构成现有技术。
发明内容
本申请提供一种聚噻吩导电聚合物、正极浆料、正极极片及其制备方法、电池单体、电池和用电装置，其能使电池兼顾高能量密度和良好的倍率性能。
本申请第一方面提供一种聚噻吩导电聚合物，包括：式(1)所示的第一结构单元；以及式(2)所示的第二结构单元、式(3)所示的第三结构单元和式(4)所示的第四结构单元中的至少一者。
R11包括C1-C8烷基或C1-C8烷基烷氧基，R12包括氢原子或C1-C3烷基；R21包括C1-C5亚烷基，R22包括氢原子或C1-C3烷基，M包括一价金属；R31包括C1-C5亚烷基，R32包括氢原子或C1-C3烷基；R41包括C1-C5亚烷基，R42包括二异氰酸酯的残基，R43包括C2-C6亚烷基，R44包括C1-C3烷基，R45包括氢原子或C1-C3烷基，s≥1；n1＞0；n2≥0，n3≥0，n4≥0，且n2+n3+n4＞0。
通过使正极极片包括本申请的聚噻吩导电聚合物，可以提升正极极片的内聚力和粘结力、提升正极极片的电解液浸润性、改善正极极片的加工性能和动力学性能，进而可以使电池兼顾高能量密度和良好的倍率性能。
在任意实施例中，所述聚噻吩导电聚合物的数均分子量为3000-45000，可选为5000-34000。聚噻吩导电聚合物的数均分子量在上述范围内时，可以使正极极片具有良好的柔韧性，由此可以改善正极极片和电池的加工性能；另外，还可以使正极浆料具有良好的分散性，由此可以更好地改善电池的性能。
在任意实施例中，所述聚噻吩导电聚合物满足如下条件(1)至(13)中的至少一者：
(1)R11包括C4-C6烷基或C4-C6烷基烷氧基；
(2)R12包括氢原子；
(3)R21包括C1-C3亚烷基；
(4)R22包括氢原子；
(5)M包括Li和/或Na；
(6)R31包括C1-C3亚烷基；
(7)R32包括氢原子；
(8)R41包括C1-C3亚烷基；
(9)R42包括Ra取代或未取代的C1-C6亚烷基、以及如下基团中的一种：
#表示连接位置，Ra分别独立地包括C1-C3烷基，Rb分别独立地包括C1-C3烷基，p表示0-4的整数，q表示0-6的整数；
(10)R43包括如下基团：
(11)R44包括甲基；
(12)R45包括氢原子；
(13)s为3-140，可选为10-90。
在任意实施例中，n2＞0，n3＝0，n4＝0；或者，n2＝0，n3＞0，n4＝0；或者，n2＝0，n3＞0，n4＞0；或者，n2＞0，n3＞0，n4＞0。
本申请第二方面提供一种正极浆料，包括溶剂以及非溶剂组分，所述非溶剂组分包括正极活性材料、正极粘结剂以及正极导电剂，所述正极导电剂包括本申请第一方面的聚噻吩导电聚合物。
在任意实施例中，所述溶剂包括非水溶剂，可选为包括N-甲基吡咯烷酮，所述正极粘结剂包括油性粘结剂，且0.35≤n1/(n1+n2+n3+n4)≤0.65；可选地，0.40≤n1/(n1+n2+n3+n4)≤0.60。n1/(n1+n2+n3+n4)在上述范围内时，可以提升非水性正极浆料的分散性，提升制备的正极极片的加工性能，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括聚偏氟乙烯、聚酰亚胺、聚氨酯中的一种或多种。
在任意实施例中，所述正极粘结剂包括油性粘结剂，且0≤n2/(n1+n2+n3+n4)≤0.25，可选地，0≤n2/(n1+n2+n3+n4)≤0.10。由此可以提升非水性正极浆料的分散性，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括油性粘结剂，且0.35≤(n3+n4)/(n1+n2+n3+n4)≤0.65，可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60。(n3+n4)/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括油性粘结剂，且0≤n4/(n3+n4)≤0.20，可选地，0＜n4/(n3+n4)≤0.15。n4/(n3+n4)在上述范围内时，可以提高正极极片和电池的加工性能，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述溶剂包括水，所述正极粘结剂包括水性粘结剂，且0.05≤n1/(n1+n2+n3+n4)≤0.25；可选地，0.08≤n1/(n1+n2+n3+n4)≤0.22。n1/(n1+n2+n3+n4)在上述范围内时，可以提升水性正极浆料的分散性，提升制备的正极极片的粘结力和加工性能，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括羧甲基纤维素及其衍生物、海藻酸钠、聚丙烯酸及其衍生物、琼脂糖、明胶、卡拉胶、黄原胶、瓜尔胶、聚乙烯醇、聚丙烯酰胺中的一种或多种。
在任意实施例中，所述正极粘结剂包括水性粘结剂，且0.15≤n2/(n1+n2+n3+n4)≤0.45，可选地，0.25≤n2/(n1+n2+n3+n4)≤0.40。n2/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括水性粘结剂，且0.30≤(n3+n4)/(n1+n2+n3+n4)≤0.80，可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60。(n3+n4)/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括水性粘结剂，且0≤n4/(n3+n4)≤0.20，可选地，0.04≤n4/(n3+n4)≤0.15。n4/(n3+n4)在上述范围内时，可以提高正极极片和电池的加工性能，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极活性材料包括锂过渡金属氧化物、含锂磷酸盐、及其各自的改性化合物中的一种或多种。
在任意实施例中，所述正极浆料还包括第二导电剂，所述第二导电剂包括超导碳、导电石墨、乙炔黑、碳黑、科琴黑、碳点、碳纳米管、石墨烯和碳纳米纤维中的一种或多种。
在任意实施例中，所述非溶剂组分中的所述聚噻吩导电聚合物的含量为0.2-4％，可选为0.5-3％，基于所述非溶剂组分的总重量计。
本申请第三方面提供一种正极极片，包括正极集流体以及设置在所述正极集流体至少一个表面上的正极膜层，所述正极膜层包括正极活性材料、正极粘结剂以及正极导电剂，所述正极导电剂包括本申请第一方面的聚噻吩导电聚合物。
在任意实施例中，所述正极粘结剂包括油性粘结剂，且0.35≤n1/(n1+n2+n3+n4)≤0.65；可选地，0.40≤n1/(n1+n2+n3+n4)≤0.60。n1/(n1+n2+n3+n4)在上述范围内时，可以提升正极膜层的均一性，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括聚偏氟乙烯、聚酰亚胺、聚氨酯中的一种或多种。
在任意实施例中，所述正极粘结剂包括油性粘结剂，且0≤n2/(n1+n2+n3+n4)≤0.25，可选地，0≤n2/(n1+n2+n3+n4)≤0.10。由此可以提升正极膜层的均一性，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括油性粘结剂，且0.35≤(n3+n4)/(n1+n2+n3+n4)≤0.65，可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60。(n3+n4)/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括油性粘结剂，且0≤n4/(n3+n4)≤0.20，可选地，0＜n4/(n3+n4)≤0.15。n4/(n3+n4)在上述范围内时，可以提高正极极片和电池的加工性能，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括水性粘结剂，且0.05≤n1/(n1+n2+n3+n4)≤0.25；可选地，0.08≤n1/(n1+n2+n3+n4)≤0.22。 n1/(n1+n2+n3+n4)在上述范围内时，可以提升正极膜层的均一性，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括羧甲基纤维素及其衍生物、海藻酸钠、聚丙烯酸及其衍生物、琼脂糖、明胶、卡拉胶、黄原胶、瓜尔胶、聚乙烯醇、聚丙烯酰胺中的一种或多种。
在任意实施例中，所述正极粘结剂包括水性粘结剂，且0.15≤n2/(n1+n2+n3+n4)≤0.45，可选地，0.25≤n2/(n1+n2+n3+n4)≤0.40。n2/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括水性粘结剂，且0.30≤(n3+n4)/(n1+n2+n3+n4)≤0.80，可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60。(n3+n4)/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极粘结剂包括水性粘结剂，且0≤n4/(n3+n4)≤0.20，可选地，0.04≤n4/(n3+n4)≤0.15。n4/(n3+n4)在上述范围内时，可以提高正极极片和电池的加工性能，还可以改善正极极片和电池的动力学性能。
在任意实施例中，所述正极活性材料包括锂过渡金属氧化物、含锂磷酸盐、及其各自的改性化合物中的一种或多种。
在任意实施例中，所述正极极片还包括第二导电剂，所述第二导电剂包括超导碳、导电石墨、乙炔黑、碳黑、科琴黑、碳点、碳纳米管、石墨烯和碳纳米纤维中的一种或多种。
在任意实施例中，所述正极膜层中的所述聚噻吩导电聚合物的含量为0.2-4％，可选为0.5-3％，基于所述正极膜层的总重量计。
本申请第四方面提供一种正极极片的制备方法，包括如下步骤：将本申请第二方面的正极浆料涂布在正极集流体至少一个表面上，干燥、辊压后获得初始正极极片；使用激光照射所获得的初始正极极片，结束后获得正极极片，所述激光波长为445-505nm。
通过将上述聚噻吩导电聚合物用于正极极片中，并通过蓝光照射正极极片，可以快速进行光热转换、提高加热效率，还可以降低蓝光照射对正极活性材料的不利影响。
通过蓝光照射可以使聚噻吩导电聚合物被快速加热，由此可以释放部分应力，从而有利于形成孔隙率较高的正极膜层，进而可以降低残余的溶剂量，还可以提升正极极片的电解液浸润性。通过蓝光照射还可以去除正极极片加工过程中引入的分散剂与表面活性剂等物质，同时加热效率高，且加热温度通常高于正极粘结剂的软化点，由此还使得正极粘结剂可以在正极极片厚度方向均匀分布，从而有助于提升正极极片的内聚力和粘结力、降低正极电阻，进而可以提升电池的倍率性能。
在任意实施例中，激光发生方式为连续发射。
在任意实施例中，激光器的数量为1-10，总功率为100-2500W。
在任意实施例中，所述初始正极极片经过激光器光斑的时间为0.05-0.5s。
在任意实施例中，激光器与所述初始正极极片的垂直距离为5-15cm。
本申请第五方面提供一种电池单体，包括本申请第三方面的正极极片或通过本申请第四方面的制备方法制备得到的正极极片。
本申请第六方面提供一种电池，包括本申请第五方面的电池单体。
本申请第七方面提供一种用电装置，其包括本申请第六方面的电池。
本申请的用电装置包括本申请提供的电池，因而至少具有与所述电池相同的优势。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍。显而易见地，下面所描述的附图仅仅是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。
图1是本申请一些实施例提供的电池单体的结构示意图。
图2是本申请一些实施例提供的电池单体的分解示意图。
图3是本申请一些实施例提供的电池模块的结构示意图。
图4是本申请一些实施例提供的电池包的结构示意图。
图5是图4所示的电池包的分解示意图。
图6是本申请一些实施例提供的用电装置的示意图。
图7是实施例1-1和对比例1-1的电池在不同倍率下的放电曲线。
在附图中，附图未必按照实际的比例绘制。附图标记说明如下：1、电池包；2、上箱体；3、下箱体；4、电池模块；5、电池单体；51、壳体；52、电极组件；53、盖板。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的聚噻吩导电聚合物、正极浆料、正极极片及其制备方法、电池单体、电池和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案，并且这样的技术方案应被认为包含在本申请的公开内容中。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案，并且这样的技术方案应被认为包含在本申请的公开内容中。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，所述提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，在本申请中，术语“第一”、“第二”、“第三”、“第四”等是用于区别不同对象，而不是用于描述特定顺序或主次关系。
在本申请中，术语“多个”、“多种”是指两个或两种以上。
除非另有说明，本申请中使用的术语具有本领域技术人员通常所理解的公知含义。
除非另有说明，本申请中提到的各参数的数值可以用本领域常用的各种测试方法进行测定，例如，可以按照本申请的实施例中给出的测试方法进行测定。除非另有说明，各参数的测试温度均为25℃。
术语“烷基”涵盖直链烷基和支链烷基。
术语“亚烷基”涵盖直链亚烷基和支链亚烷基。
术语“烷基烷氧基”涵盖直链烷基烷氧基和支链烷基烷氧基。
术语“氢原子”涵盖1H(H)、2H(D)和3H(T)。
在本说明书的各处，“#”出现时表示连接位置。
在本说明书的各处，单键穿过环或环体系的表示方法是指单键可以连接在该环或环体系的任意可接入位置。
在本说明书的各处，化合物的取代基以组或范围公开。明确地预期这种描述包括这些组和范围的成员的每一个单独的子组合。例如，明确地预期术语“C1-C6烷基”单独地公开C1、C2、C3、C4、C5、C6、C1-C6、C1-C5、C1-C4、C1-C3、C1-C2、C2-C6、C2-C5、C2-C4、C2-C3、C3-C6、C3-C5、C3-C4、C4-C6、C4-C5、C5-C6烷基。作为其它实例，明确地预期范围为3-10的整数单独地公开3、4、5、6、7、8、9和10。据此，可明确地预期其它组或范围。
本申请的实施例中所提到的电池可以为包括一个或多个电池单体以提供更高的电压和容量的单一的物理模块。例如，本申请中所提到的电池可包括电池单体、电池模块或电池包等。
电池单体是组成电池的最小单元，其独自能够实现充放电的功能。电池单体可呈圆柱体、长方体或其它形状等，本申请实施例对此并不限定。如图1是作为一个示例的长方体结构的电池单体5。
电池单体有多个时，多个电池单体通过汇流部件串联、并联或混联。在一些实施例中，电池可以为电池模块；电池单体有多个时，多个电池单体排列并固定形成一个电池模块。在一些实施例中，电池可以为电池包，电池包包括箱体和电池单体，电池单体或 电池模块容纳于箱体中。在一些实施例中，箱体可以作为车辆的底盘结构的一部分。例如，箱体的部分可以成为车辆的底板的至少一部分，或者，箱体的部分可以成为车辆的横梁和纵梁的至少一部分。
在一些实施例中，电池可以为储能装置。储能装置包括储能集装箱、储能电柜等。
本申请的实施例提供的电池单体包括锂离子电池单体、锂金属电池单体等，本申请实施例对此并不限定。
电池单体一般包括电极组件和电解质。电极组件通常包括正极极片和负极极片，电极组件可以是卷绕式结构，也可以是叠片式结构，本申请实施例对此并不限定。
电池单体还可包括外包装，外包装可用于封装电极组件和电解质。外包装可以是硬壳，例如硬塑料壳、铝壳、钢壳等。外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，如聚丙烯(PP)、聚对苯二甲酸丁二醇酯(PBT)和聚丁二酸丁二醇酯(PBS)中的一种或多种。
在一些实施例中，如图2所示，外包装可包括壳体51和盖板53。壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53用于盖设开口，以封闭容纳腔。电极组件52封装于容纳腔。电池单体5所含电极组件52的数量可以为一个或多个，可根据需求来调节。
在一些实施例中，电池单体可以组装成电池模块，电池模块所含电池单体的数量可以为多个，具体数量可根据电池模块的应用和容量来调节。图3是作为一个示例的电池模块4的示意图。如图3所示，在电池模块4中，多个电池单体5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个电池单体5进行固定。
可选地，电池模块4还可包括具有容纳空间的外壳，多个电池单体5容纳于该容纳空间。
在一些实施例中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以根据电池包的应用和容量进行调节。
图4和图5是作为一个示例的电池包1的示意图。如图4和图5所示，在电池包1中可包括箱体和设置于箱体中的多个电池模块4。箱体包括上箱体2和下箱体3，上箱体2用于盖设下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于箱体中。
正极极片作为电池的重要组成部件，其性能好坏对电池性能的影响至关重要。
为了进一步提升电池的能量密度，目前通常采用的做法是制备厚涂布的正极极片，或者制备高压实密度的正极极片。但是，厚涂布和/或高压实密度的正极极片的柔韧性和加工性能通常较差，在弯折、卷绕或者电极组件热压时，容易出现正极膜层开裂或者部分正极膜层从正极集流体表面脱落(即掉粉)等问题；并且正极极片中残余的溶剂(例如水、N-甲基吡咯烷酮等)还难以充分去除，由此还使得正极膜层的电解液浸润性较差，难以使电解液充分分布在正极膜层中，进而还影响了电池的倍率性能。
因此，如何使电池在具有高能量密度的前提下，还具备良好的加工性能和倍率性能仍是目前需要解决的技术难题。
鉴于此，发明人提出了一种新的聚噻吩导电聚合物，将其用于正极极片中，经过激 光照射处理后，可以提升正极极片的加工性能，还可以使电池兼顾高能量密度和良好的倍率性能。
[聚噻吩导电聚合物]
本申请实施例提供的聚噻吩导电聚合物包括式(1)所示的第一结构单元以及式(2)所示的第二结构单元、式(3)所示的第三结构单元和式(4)所示的第四结构单元中的至少一者。
R11包括C1-C8烷基或C1-C8烷基烷氧基，R12包括氢原子或C1-C3烷基。
R21包括C1-C5亚烷基，R22包括氢原子或C1-C3烷基，M包括一价金属。
R31包括C1-C5亚烷基，R32包括氢原子或C1-C3烷基。
R41包括C1-C5亚烷基，R42包括二异氰酸酯的残基，R43包括C2-C6亚烷基，R44包括C1-C3烷基，R45包括氢原子或C1-C3烷基，s≥1。R42包括二异氰酸酯的残基，即可以为二异氰酸酯O＝C＝N—R42—N＝C＝O去掉两端的异氰酸酯基后的剩余基团。
n1＞0。
n2≥0，n3≥0，n4≥0，且n2+n3+n4＞0。
为了降低正极电阻，目前通常采用的做法是在配制正极浆料时提高正极导电剂，例如导电碳的用量，由此不仅可以降低正极膜层的整体电阻，而且可以改善电池的倍率性能。但是，对于高能量密度电池体系而言，由于正极极片的涂布重量大、压实密度高，导电碳的分散均匀性变差，因此采用上述方法对于电池内阻和倍率性能的改善作用有限，同时正极极片和电池的加工性能仍比较差。
发明人研究发现，通过使正极极片包括本申请实施例提供的聚噻吩导电聚合物，可以提升正极极片的内聚力和粘结力、提升正极极片的电解液浸润性、改善正极极片的加工性能和动力学性能，进而可以使电池兼顾高能量密度和良好的倍率性能。
正极极片中的正极活性材料对于蓝光的吸收率较低，而本申请实施例提供的聚噻吩导电聚合物则具有较高的蓝光吸收能力，因此，通过将本申请实施例提供的聚噻吩导电聚合物用于正极极片中，并通过蓝光照射正极极片，可以快速进行光热转换、提高加热效率，还可以降低蓝光照射对正极活性材料的不利影响。
本申请实施例提供的聚噻吩导电聚合物具有良好的导热性，将其用于正极极片并经蓝光照射正极极片时，聚噻吩导电聚合物可以被快速加热，由此可以释放部分应力，从而有利于形成孔隙率较高的正极膜层，进而可以降低残余的溶剂量，还可以提升正极极片的电解液浸润性；加热时还可以软化正极粘结剂，使聚噻吩导电聚合物和正极粘结剂 更均匀地分布在正极膜层中，由此可以增加正极极片的内聚力和粘结力，并还可以降低正极电阻，进而可以提升正极极片和电池的动力学性能。
本申请实施例提供的聚噻吩导电聚合物包括式(2)所示的第二结构单元、式(3)所示的第三结构单元和式(4)所示的第四结构单元中的至少一者，式(2)所示的第二结构单元、式(3)所示的第三结构单元、式(4)所示的第四结构单元具有强极性基团，例如羟基、酯基、氨基甲酸酯基等，这些强极性基团可以使聚噻吩导电聚合物的吸光波长红移，由此可以减少HOMO轨道与LUMO轨道的电化学带隙，进而可以增加聚噻吩导电聚合物的最大吸收峰出现位置，提高加热效率。本申请实施例提供的聚噻吩导电聚合物还包括式(1)所示的第一结构单元，由此既可以使正极膜层具有良好的电解液浸润性，又可以避免聚噻吩导电聚合物溶解。
本申请实施例提供的聚噻吩导电聚合物用于正极膜层后，还可以改善正极极片，特别是厚涂布和/或高压实密度的正极极片的柔韧性和加工性能。另外，本申请实施例提供的聚噻吩导电聚合物具有导电性，用于正极极片中时，还可以提供良好的电子导电通路。
因此，本申请实施例提供的聚噻吩导电聚合物可以提高正极极片的加工性能，提高正极极片的内聚力和粘结力，还可以降低正极电阻，将其用于电池时，可以获得兼顾高能量密度和良好的倍率性能的电池。
本申请实施例提供的聚噻吩导电聚合物包括式(1)所示的第一结构单元以及式(2)所示的第二结构单元、式(3)所示的第三结构单元和式(4)所示的第四结构单元中的至少一者。例如，在一些实施例中，聚噻吩导电聚合物包括式(1)所示的第一结构单元和式(2)所示的第二结构单元，此时，n2＞0，n3＝0，n4＝0；在一些实施例中，聚噻吩导电聚合物包括式(1)所示的第一结构单元和式(3)所示的第三结构单元，此时，n2＝0，n3＞0，n4＝0；在一些实施例中，聚噻吩导电聚合物包括式(1)所示的第一结构单元、式(3)所示的第三结构单元和式(4)所示的第四结构单元，此时，n2＝0，n3＞0，n4＞0；在一些实施例中，聚噻吩导电聚合物包括式(1)所示的第一结构单元、式(2)所示的第二结构单元、式(3)所示的第三结构单元和式(4)所示的第四结构单元，此时，n2＞0，n3＞0，n4＞0。
在一些实施例中，聚噻吩导电聚合物的数均分子量可以为3000-45000，例如，可以为3000、4000、5000、7600、8600、10000、12000、15000、18000、20500、23000、25200、28000、30000、34000、40000、45000、或上述任意数值组成的范围。在一些实施例中，可选地，聚噻吩导电聚合物的数均分子量可以为5000-34000，7600-34000，10000-34000，5000-30000，7600-30000，10000-30000，5000-28000，7600-28000，10000-28000，5000-25200，7600-25200，10000-25200。
聚噻吩导电聚合物的数均分子量在上述范围内时，可以使正极极片具有良好的柔韧性，由此可以改善正极极片和电池的加工性能；另外，还可以使正极浆料具有良好的分散性，并可以避免聚噻吩导电聚合物在电解液中溶解，由此可以更好地改善电池的性能。
聚噻吩导电聚合物的数均分子量在上述范围内时，还可以使聚噻吩导电聚合物具有良好的导热性和电子电导性，由此既可以提高加热效率，又可以降低正极电阻。
聚噻吩导电聚合物的数均分子量具有本领域公知的含义，可以用本领域已知的仪器和方法进行测试，例如可以通过凝胶渗透色谱法(GPC)进行测试。
在一些实施例中，R11可以包括C4-C6烷基或C4-C6烷基烷氧基。
在一些实施例中，R12可以包括氢原子。
在一些实施例中，R11包括C4-C6烷基或C4-C6烷基烷氧基，R12包括氢原子。
在一些实施例中，R21可以包括C1-C3亚烷基。
在一些实施例中，R22可以包括氢原子。
在一些实施例中，M可以包括Li和/或Na。
在一些实施例中，R21包括C1-C3亚烷基，R22包括氢原子，M包括Li和/或Na。
在一些实施例中，R31可以包括C1-C3亚烷基。
在一些实施例中，R32可以包括氢原子。
在一些实施例中，R31包括C1-C3亚烷基，R32包括氢原子。
在一些实施例中，R41可以包括C1-C3亚烷基。
在一些实施例中，R42可以表示脂肪族、脂环族和/或芳香族二异氰酸酯的残基。可选地，R42包括Ra取代或未取代的C1-C6亚烷基、以及如下基团中的一种：
#表示连接位置，Ra分别独立地包括C1-C3烷基，Rb分别独立地包括C1-C3烷基，p表示0-4的整数，q表示0-6的整数。p为0时，表示该位置未发生取代。q为0时，表示该位置未发生取代。
在一些实施例中，R43可以包括如下基团：
在一些实施例中，R44可以包括甲基。
在一些实施例中，R45可以包括氢原子。
在一些实施例中，s可以为3-140，例如，可以为3、10、15、20、25、30、40、50、60、70、80、90、100、110、120、130、140、或上述任意数值组成的范围。在一些实施例中，可选地，s可以为10-90，10-80，10-70，10-60，10-50，20-90，20-80，20-70，20-60，20-50，25-90，25-80，25-70，25-60，25-50。
[聚噻吩导电聚合物的制备方法]
本申请实施例还提供一种制备上述聚噻吩导电聚合物的方法。
所述方法至少包括步骤：提供用于制备聚噻吩导电聚合物的单体化合物或其前体化合物；将单体化合物或其前体化合物通过氧化聚合法制备得到聚噻吩导电聚合物。氧化聚合法可以为化学氧化聚合法或电化学氧化聚合法。作为示例，化学氧化聚合法的氧化剂可以为FeCl3。
本领域技术人员可以根据目标产物选择合适的单体化合物或其前体化合物。
例如，用于形成第一结构单元的第一单体化合物可以为
作为示例，第一单体化合物可以包括3-丁氧基噻吩、3-戊氧基噻吩中的一种或多种。
第一单体化合物可以使用甲氧基噻吩作为原料通过烷基链置换得到。在一些实施例中，在氮气环境中，将甲氧基噻吩、醇(例如正丁醇、正戊醇等)、无水硫酸氢钠、甲苯依次加入反应体系中于80-100℃加热搅拌2-5h，经减压蒸馏得到第一单体化合物。
用于形成第二结构单元的第二单体化合物可以为或其前体化合物R23包括C1-C8烷基。
作为示例，第二单体化合物可以包括噻吩-3-氧基乙酸钠、噻吩-3-氧基乙酸锂、2-(噻吩-3-氧基)丙酸钠、2-(噻吩-3-氧基)丙酸锂、3-(噻吩-3-氧基)丙酸钠、3-(噻吩-3-氧基)丙酸锂中的一种或多种，第二单体化合物的前体化合物可以包括噻吩-3-氧基乙酸甲酯、噻吩-3-氧基乙酸乙酯、2-(噻吩-3-氧基)丙酸甲酯、2-(噻吩-3-氧基)丙酸乙酯、3-(噻吩-3-氧基)丙酸甲酯、3-(噻吩-3-氧基)丙酸乙酯中的一种或多种。
第二单体化合物的前体化合物可以使用甲氧基噻吩作为原料通过烷基链置换得到。在一些实施例中，在氮气环境中，将甲氧基噻吩、酯(例如乙醇酸甲酯、乙醇酸乙酯、乳酸甲酯、乳酸乙酯、β-羟基丙酸甲酯、β-羟基丙酸乙酯等)、无水硫酸氢钠、甲苯依次加入反应体系中于80-100℃加热搅拌2-5h，经减压蒸馏得到第二单体化合物的前体化合物。
第二单体化合物可以将第二单体化合物的前体化合物置于碱性溶液中，调节pH，搅拌反应后得到第二单体化合物。碱性溶液可以包括MOH，M包括一价金属，可选为包括Li和/或Na。
用于形成第三结构单元的第三单体化合物可以为
作为示例，第三单体化合物可以包括3-噻吩甲醇、3-噻吩乙醇中的一种或多种。
用于形成第四结构单元的第四单体化合物可以为
第四单体化合物可以通过以下方法制备得到：在氮气环境下，将OH—(R43)s—O—R44、二异氰酸酯OCN—R42—NCO溶于溶剂(例如N,N-二甲基甲酰胺)中，于70℃搅拌反应1-4h，随后加入继续在氮气保护下于70℃搅拌反应4-8h，得到第四单体化合物。
OH—(R43)s—O—R44可以包括聚乙二醇单甲醚(MPEG)、聚丁二醇单甲醚。
在一些实施例中，所述方法包括步骤：将单体化合物或其前体化合物溶于氯仿中，然后在氮气保护下加入至无水FeCl3的氯仿溶液中，在20-25℃下进行聚合反应(例如24-96h)，之后加入甲醇使聚合产物沉淀，最后将沉淀物在乙醇中进行抽提(例如24-96h)，经干燥后得到聚噻吩导电聚合物。
在一些实施例中，所述方法包括步骤：将第一单体化合物、第二单体化合物和第三单体化合物溶于氯仿中，然后在氮气保护下加入至无水FeCl3的氯仿溶液中，在20-25℃下进行聚合反应(例如24-96h)，之后加入甲醇使聚合产物沉淀，最后将沉淀物在乙醇中进行抽提(例如24-96h)；在氮气环境下，将OH—(R43)s—O—R44、二异氰酸酯OCN—R42—NCO溶于溶剂(例如N,N-二甲基甲酰胺)中，于65-75℃搅拌反应1-4h，随后加入上述沉淀物溶液(溶剂可以为N,N-二甲基甲酰胺)，继续在氮气保护下于65-75℃搅拌反应4-8h，之后用乙醇抽提(例如12-48h)，经真空干燥，得到聚噻吩导电聚合物。聚噻吩导电聚合物包括第一结构单元、第二结构单元、第三结果单元和第四结构单元。
在一些实施例中，所述方法包括步骤：将第一单体化合物、第二单体化合物的前体化合物和第三单体化合物溶于氯仿中，然后在氮气保护下加入至无水FeCl3的氯仿溶液中，在20-25℃下进行聚合反应(例如24-96h)，之后加入甲醇使聚合产物沉淀，最后将沉淀物在乙醇中进行抽提(例如24-96h)；在氮气环境下，将OH—(R43)s—O—R44、二异氰酸酯OCN—R42—NCO溶于溶剂(例如N,N-二甲基甲酰胺)中，于65-75℃搅拌反应1-4h，随后加入上述沉淀物溶液(溶剂可以为N,N-二甲基甲酰胺)，继续在氮气保护下于65-75℃搅拌反应4-8h，之后用乙醇抽提(例如12-48h)，真空干燥后，将产物分散于水中，加入MOH调节体系的pH(例如7-9)，搅拌反应后得到聚噻吩导电聚合物。聚噻吩导电聚合物包括第一结构单元、第二结构单元、第三结果单元和第四结构单元。
通过调节单体的种类及浓度、氧化剂的种类及浓度、反应温度、反应时间等参数，可以获得不同分子量的聚噻吩导电聚合物。
[正极浆料]
本申请实施例还提供一种正极浆料。
正极浆料包括溶剂以及非溶剂组分，非溶剂组分包括正极活性材料、正极粘结剂以及正极导电剂，正极导电剂包括本申请如上的聚噻吩导电聚合物。
本申请实施例提供的聚噻吩导电聚合物既可以用于非水性正极浆料中，也可以用于水性正极浆料中。
在一些实施例中，溶剂包括非水溶剂，可选为包括N-甲基吡咯烷酮，正极粘结剂包括油性粘结剂，且0.35≤n1/(n1+n2+n3+n4)≤0.65。例如，n1/(n1+n2+n3+n4)可以为0.35、0.40、0.45、0.50、0.55、0.60、0.65、或上述任意数值组成的范围。
可选地，0.40≤n1/(n1+n2+n3+n4)≤0.60。
n1/(n1+n2+n3+n4)在上述范围内时，可以提升非水性正极浆料的分散性，提升制备的正极极片的加工性能，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括油性粘结剂，作为示例，正极粘结剂可以包括聚偏氟乙烯、聚酰亚胺、聚氨酯中的一种或多种。聚偏氟乙烯的重均分子量可以为5万-200万，由此可以提升正极极片的粘结力，还可以提升正极极片的加工性能。
在一些实施例中，正极粘结剂包括油性粘结剂，0≤n2/(n1+n2+n3+n4)≤0.25，例如，n2/(n1+n2+n3+n4)可以为0、0.05、0.10、0.15、0.20、0.25、或上述任意数值组成的范围。
在一些实施例中，正极粘结剂包括油性粘结剂，0≤n2/(n1+n2+n3+n4)≤0.10，可选地，n2/(n1+n2+n3+n4)＝0。
由此可以提升非水性正极浆料的分散性，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括油性粘结剂，0.35≤(n3+n4)/(n1+n2+n3+n4)≤0.65，例如，(n3+n4)/(n1+n2+n3+n4)可以为0.35、0.40、0.45、0.50、0.55、0.60、0.65、或上述任意数值组成的范围。
可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60。
(n3+n4)/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在一些实施例中，0≤n4/(n3+n4)≤0.20，例如，n4/(n3+n4)可以为0、0.05、0.10、0.12、0.15、0.20、或上述任意数值组成的范围。
可选地，0＜n4/(n3+n4)≤0.15，0＜n4/(n3+n4)≤0.12。
n4/(n3+n4)在上述范围内时，可以提高正极极片和电池的加工性能，还可以改善正极极片和电池的动力学性能。
在一些实施例中，溶剂包括非水溶剂，可选为包括N-甲基吡咯烷酮，正极粘结剂包括油性粘结剂，且0.35≤n1/(n1+n2+n3+n4)≤0.65，0≤n2/(n1+n2+n3+n4)≤0.25，0.35≤(n3+n4)/(n1+n2+n3+n4)≤0.65，0＜n4/(n3+n4)≤0.15。
在一些实施例中，溶剂包括非水溶剂，可选为包括N-甲基吡咯烷酮，正极粘结剂包括油性粘结剂，且0.40≤n1/(n1+n2+n3+n4)≤0.60，0≤n2/(n1+n2+n3+n4)≤0.10，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0＜n4/(n3+n4)≤0.15。
在一些实施例中，溶剂包括非水溶剂，可选为包括N-甲基吡咯烷酮，正极粘结剂包括油性粘结剂，且0.40≤n1/(n1+n2+n3+n4)≤0.60，n2/(n1+n2+n3+n4)＝0，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0＜n4/(n3+n4)≤0.15。
在一些实施例中，溶剂包括水，正极粘结剂包括水性粘结剂，且0.05≤n1/(n1+n2+n3+n4)≤0.25。例如，n1/(n1+n2+n3+n4)可以为0.05、0.08、0.11、0.15、0.20、0.22、0.25、或上述任意数值组成的范围。
可选地，0.08≤n1/(n1+n2+n3+n4)≤0.22，0.11≤n1/(n1+n2+n3+n4)≤0.22。
n1/(n1+n2+n3+n4)在上述范围内时，可以提升水性正极浆料的分散性，提升制备的正极极片的粘结力和加工性能，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括水性粘结剂，作为示例，正极粘结剂可以包括羧甲基纤维素及其衍生物、海藻酸钠、聚丙烯酸及其衍生物、琼脂糖、明胶、卡拉胶、黄原胶、瓜尔胶、聚乙烯醇、聚丙烯酰胺中的一种或多种。正极粘结剂在上述范围内时，一方面对环境更友好，另一方面还可以提升正极膜层的电解液亲和性。
在一些实施例中，正极粘结剂包括水性粘结剂，0.15≤n2/(n1+n2+n3+n4)≤0.45，例如，n2/(n1+n2+n3+n4)可以为0.15、0.20、0.25、0.30、0.36、0.40、0.45、或上述任意数值组成的范围。
可选地，0.25≤n2/(n1+n2+n3+n4)≤0.40，0.25≤n2/(n1+n2+n3+n4)≤0.36。
n2/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括水性粘结剂，0.30≤(n3+n4)/(n1+n2+n3+n4)≤0.80，例如，(n3+n4)/(n1+n2+n3+n4)可以为0.30、0.35、0.40、0.42、0.45、0.50、0.55、0.60、0.65、0.70、0.75、0.80、或上述任意数值组成的范围。
可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0.42≤(n3+n4)/(n1+n2+n3+n4)≤0.60。
(n3+n4)/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括水性粘结剂，0≤n4/(n3+n4)≤0.20，例如，n4/(n3+n4)可以为0、0.03、0.04、0.05、0.08、0.10、0.12、0.15、0.20、或上述任意数值组成的范围。
可选地，0.04≤n4/(n3+n4)≤0.15。
n4/(n3+n4)在上述范围内时，可以提高正极极片和电池的加工性能，还可以改善正极极片和电池的动力学性能。
在一些实施例中，溶剂包括水，正极粘结剂包括水性粘结剂，且0.05≤n1/(n1+n2+n3+n4)≤0.25，0.15≤n2/(n1+n2+n3+n4)≤0.45，0.30≤(n3+n4)/(n1+n2+n3+n4)≤0.80，0.04≤n4/(n3+n4)≤0.15。
在一些实施例中，溶剂包括水，正极粘结剂包括水性粘结剂，且0.08≤n1/(n1+n2+n3+n4)≤0.22，0.25≤n2/(n1+n2+n3+n4)≤0.40，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0.04≤n4/(n3+n4)≤0.15。
在一些实施例中，溶剂包括水，正极粘结剂包括水性粘结剂，且0.11≤n1/(n1+n2+n3+n4)≤0.22，0.25≤n2/(n1+n2+n3+n4)≤0.36，0.42≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0.04≤n4/(n3+n4)≤0.15。
在一些实施例中，正极活性材料可以包括锂过渡金属氧化物、含锂磷酸盐、及其各自的改性化合物中的一种或多种。锂过渡金属氧化物的示例可包括锂钴氧化物、锂镍氧 化物、锂锰氧化物、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物、锂镍钴铝氧化物、及其各自的改性化合物中的一种或多种。含锂磷酸盐的示例可包括磷酸铁锂、磷酸铁锂与碳的复合材料、磷酸锰锂、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料、及其各自的改性化合物中的一种或多种。本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统公知的材料。
在一些实施例中，正极活性材料可以包括含锂磷酸盐，可选地包括磷酸铁锂、磷酸锰锂、磷酸锰铁锂、及其各自的改性化合物中的一种或多种。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
上述各正极活性材料的改性化合物可以是对正极活性材料进行掺杂改性和/或表面包覆改性。
在一些实施例中，正极浆料还可以包括第二导电剂。作为示例，第二导电剂可以包括超导碳、导电石墨、乙炔黑、碳黑、科琴黑、碳点、碳纳米管、石墨烯和碳纳米纤维中的一种或多种。
在一些实施例中，非溶剂组分中的聚噻吩导电聚合物的含量可以为0.2-4％，可选为0.5-3％，基于非溶剂组分的总重量计。
聚噻吩导电聚合物中不同结构单元的相对含量可以通过核磁共振波谱法(NMR)进行测试。
[正极极片]
本申请实施例还提供一种正极极片。
正极极片包括正极集流体以及设置在正极集流体至少一个表面上的正极膜层，正极膜层包括正极活性材料、正极粘结剂以及正极导电剂，正极导电剂包括本申请如上的聚噻吩导电聚合物。
正极集流体具有在自身厚度方向相对的两个表面，正极膜层设置在正极集流体的两个相对表面中的任意一者或两者上。
在一些实施例中，正极集流体可以采用金属箔片或复合集流体。作为金属箔片的示例，可采用铝箔。可选地，铝箔可以为1060、1070、1100或1235，纯度可以大于99％。复合集流体可包括高分子材料基层以及形成于高分子材料基层至少一个表面上的金属材料层。作为示例，金属材料可包括铝、铝合金、镍、镍合金、钛、钛合金、银和银合金中的一种或多种。作为示例，高分子材料基层可包括聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)和聚乙烯(PE)中的一种或多种。
在一些实施例中，正极集流体的厚度可以为10-20μm。
在一些实施例中，正极粘结剂包括油性粘结剂，作为示例，正极粘结剂可以包括聚偏氟乙烯、聚酰亚胺、聚氨酯中的一种或多种。聚偏氟乙烯的重均分子量可以为5万-200万，由此可以提升正极极片的粘结力，还可以提升正极极片的加工性能。
在一些实施例中，正极粘结剂包括油性粘结剂，且0.35≤n1/(n1+n2+n3+n4)≤0.65例如，n1/(n1+n2+n3+n4)可以为0.35、0.40、0.45、0.50、0.55、0.60、0.65、或上述任意数值组成的范围。
可选地，0.40≤n1/(n1+n2+n3+n4)≤0.60。
n1/(n1+n2+n3+n4)在上述范围内时，可以提升正极膜层的均一性，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括油性粘结剂，0≤n2/(n1+n2+n3+n4)≤0.25，例如，n2/(n1+n2+n3+n4)可以为0、0.05、0.10、0.15、0.20、0.25、或上述任意数值组成的范围。
在一些实施例中，正极粘结剂包括油性粘结剂，0≤n2/(n1+n2+n3+n4)≤0.10，可选地，n2/(n1+n2+n3+n4)＝0。
由此可以提升正极膜层的均一性，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括油性粘结剂，0.35≤(n3+n4)/(n1+n2+n3+n4)≤0.65，例如，(n3+n4)/(n1+n2+n3+n4)可以为0.35、0.40、0.45、0.50、0.55、0.60、0.65、或上述任意数值组成的范围。
可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60。
(n3+n4)/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括油性粘结剂，0≤n4/(n3+n4)≤0.20，例如，n4/(n3+n4)可以为0、0.05、0.10、0.12、0.15、0.20、或上述任意数值组成的范围。
可选地，0＜n4/(n3+n4)≤0.15，0＜n4/(n3+n4)≤0.12。
n4/(n3+n4)在上述范围内时，可以提高正极极片和电池的加工性能，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括油性粘结剂，且0.35≤n1/(n1+n2+n3+n4)≤0.65，0≤n2/(n1+n2+n3+n4)≤0.25，0.35≤(n3+n4)/(n1+n2+n3+n4)≤0.65，0＜n4/(n3+n4)≤0.15。
在一些实施例中，正极粘结剂包括油性粘结剂，且0.40≤n1/(n1+n2+n3+n4)≤0.60，0≤n2/(n1+n2+n3+n4)≤0.10，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0＜n4/(n3+n4)≤0.15。
在一些实施例中，正极粘结剂包括油性粘结剂，且0.40≤n1/(n1+n2+n3+n4)≤0.60，n2/(n1+n2+n3+n4)＝0，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0＜n4/(n3+n4)≤0.15。
在一些实施例中，正极粘结剂包括水性粘结剂，作为示例，正极粘结剂可以包括羧甲基纤维素及其衍生物、海藻酸钠、聚丙烯酸及其衍生物、琼脂糖、明胶、卡拉胶、黄原胶、瓜尔胶、聚乙烯醇、聚丙烯酰胺中的一种或多种。正极粘结剂在上述范围内时，一方面对环境更友好，另一方面还可以提升正极膜层的电解液亲和性。
在一些实施例中，正极粘结剂包括水性粘结剂，且0.05≤n1/(n1+n2+n3+n4)≤0.25。例如，n1/(n1+n2+n3+n4)可以为0.05、0.08、0.11、0.15、0.20、0.22、0.25、或上述任意数值组成的范围。
可选地，0.08≤n1/(n1+n2+n3+n4)≤0.22，0.11≤n1/(n1+n2+n3+n4)≤0.22。
n1/(n1+n2+n3+n4)在上述范围内时，可以提升正极膜层的均一性，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括水性粘结剂，0.15≤n2/(n1+n2+n3+n4)≤0.45，例如，n2/(n1+n2+n3+n4)可以为0.15、0.20、0.25、0.30、0.36、0.40、0.45、或上述任意数值组成的范围。
可选地，0.25≤n2/(n1+n2+n3+n4)≤0.40，0.25≤n2/(n1+n2+n3+n4)≤0.36。
n2/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括水性粘结剂，0.30≤(n3+n4)/(n1+n2+n3+n4)≤0.80，例如，(n3+n4)/(n1+n2+n3+n4)可以为0.30、0.35、0.40、0.42、0.45、0.50、0.55、0.60、0.65、0.70、0.75、0.80、或上述任意数值组成的范围。
可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0.42≤(n3+n4)/(n1+n2+n3+n4)≤0.60。
(n3+n4)/(n1+n2+n3+n4)在上述范围内时，可以提高正极极片的加热效率，提升正极极片的粘结力和内聚力，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括水性粘结剂，0≤n4/(n3+n4)≤0.20，例如，n4/(n3+n4)可以为0、0.03、0.04、0.05、0.08、0.10、0.12、0.15、0.20、或上述任意数值组成的范围。
可选地，0.04≤n4/(n3+n4)≤0.15。
n4/(n3+n4)在上述范围内时，可以提高正极极片和电池的加工性能，还可以改善正极极片和电池的动力学性能。
在一些实施例中，正极粘结剂包括水性粘结剂，且0.05≤n1/(n1+n2+n3+n4)≤0.25，0.15≤n2/(n1+n2+n3+n4)≤0.45，0.30≤(n3+n4)/(n1+n2+n3+n4)≤0.80，0.04≤n4/(n3+n4)≤0.15。
在一些实施例中，正极粘结剂包括水性粘结剂，且0.08≤n1/(n1+n2+n3+n4)≤0.22，0.25≤n2/(n1+n2+n3+n4)≤0.40，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0.04≤n4/(n3+n4)≤0.15。
在一些实施例中，正极粘结剂包括水性粘结剂，且0.11≤n1/(n1+n2+n3+n4)≤0.22，0.25≤n2/(n1+n2+n3+n4)≤0.36，0.42≤(n3+n4)/(n1+n2+n3+n4)≤0.60，0.04≤n4/(n3+n4)≤0.15。
在一些实施例中，正极导电剂还可以包括第二导电剂。作为示例，第二导电剂可以包括超导碳、导电石墨、乙炔黑、碳黑、科琴黑、碳点、碳纳米管、石墨烯和碳纳米纤维中的一种或多种。
在一些实施例中，正极膜层中的聚噻吩导电聚合物的含量可以为0.2-4％，可选为0.5-3％，基于正极膜层的总重量计。
在一些实施例中，正极膜层中的正极导电剂(包括聚噻吩导电聚合物和第二导电剂)的含量可以为0.5-4％，基于正极膜层的总重量计。
在一些实施例中，正极膜层中的正极活性材料的含量可以为92-98％，基于正极膜层的总重量计。
在一些实施例中，正极膜层中的正极粘结剂的含量可以为1-10％，基于正极膜层的总重量计。
正极活性材料可以采用本领域已知的材料，本申请实施例对此并不限定。在一些实施例中，正极活性材料包括能够可逆脱出和嵌入锂离子的材料。
在一些实施例中，正极活性材料可以包括锂过渡金属氧化物、含锂磷酸盐、及其各自的改性化合物中的一种或多种。锂过渡金属氧化物的示例可包括锂钴氧化物、锂镍氧化物、锂锰氧化物、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物、 锂镍钴铝氧化物、及其各自的改性化合物中的一种或多种。含锂磷酸盐的示例可包括磷酸铁锂、磷酸铁锂与碳的复合材料、磷酸锰锂、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料、及其各自的改性化合物中的一种或多种。本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统公知的材料。
在一些实施例中，正极活性材料可以包括含锂磷酸盐，可选地包括磷酸铁锂、磷酸锰锂、磷酸锰铁锂、及其各自的改性化合物中的一种或多种。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
上述各正极活性材料的改性化合物可以是对正极活性材料进行掺杂改性和/或表面包覆改性。
在一些实施例中，正极活性材料可以包括含锂磷酸盐，正极活性材料的体积分布粒径Dv50可以为1-10μm。
在一些实施例中，正极活性材料可以包括含锂磷酸盐，正极极片的面密度可以为0.2-0.8g/1540.25mm2。
在一些实施例中，正极活性材料可以包括含锂磷酸盐，正极极片的压实密度可以为2.2-2.5g/cm3。由此可以使电池具有高能量密度。
[正极极片的制备方法]
本申请实施例还提供一种正极极片的制备方法。
所述方法包括如下步骤：将本申请如上的正极浆料涂布在正极集流体至少一个表面上，干燥、辊压后获得初始正极极片；使用激光照射所获得的初始正极极片，结束后获得正极极片。激光波长可以为445-505nm。
正极极片中的正极活性材料对于蓝光(波长为445-505nm)的吸收率较低，而本申请实施例提供的聚噻吩导电聚合物则具有较高的蓝光吸收能力，因此，通过将本申请实施例提供的聚噻吩导电聚合物用于正极极片中，并通过蓝光照射正极极片，可以快速进行光热转换、提高加热效率，还可以降低蓝光照射对正极活性材料的不利影响。
通过蓝光照射可以使聚噻吩导电聚合物被快速加热，由此可以释放部分应力，从而有利于形成孔隙率较高的正极膜层，进而可以降低残余的溶剂量，还可以提升正极极片的电解液浸润性。通过蓝光照射还可以去除正极极片加工过程中引入的分散剂与表面活性剂等物质，同时加热效率高，且加热温度通常高于正极粘结剂的软化点，由此还使得正极粘结剂可以在正极极片厚度方向均匀分布，从而有助于提升正极极片的内聚力和粘结力、降低正极电阻，进而可以提升电池的倍率性能。
在一些实施例中，激光发生方式可以为连续发射。
在一些实施例中，激光器的数量可以为1-10，总功率可以为100-2500W。
在一些实施例中，初始正极极片经过激光器光斑的时间可以为0.05-0.5s。初始正极极片经过激光器光斑的时间是指初始正极极片相同位置从接触激光器光斑开始进行照射至离开激光器光斑停止照射的时间。
在一些实施例中，激光器与初始正极极片的垂直距离可以为5-15cm。
[负极极片]
电池单体包括负极极片。负极极片的结构和组成可以根据电池单体的种类进行选择，本申请实施例对此并不限定。
在一些实施例中，负极极片可包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，负极膜层包括负极活性材料。
负极集流体具有在自身厚度方向相对的两个表面，负极膜层设置在负极集流体的两个相对表面中的任意一者或两者上。
在一些实施例中，负极集流体可采用金属箔片或复合集流体。作为金属箔片的示例，可采用铜箔、铜合金箔、铝箔、铝合金箔。复合集流体可包括高分子材料基层以及形成于高分子材料基层至少一个表面上的金属材料层。作为示例，金属材料可包括铜、铜合金、镍、镍合金、钛、钛合金、银和银合金中的一种或多种。作为示例，高分子材料基层可包括聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)和聚乙烯(PE)中的一种或多种。
负极活性材料可采用本领域公知的材料。在一些实施例中，作为示例，负极活性材料可包括但不限于天然石墨、人造石墨、软碳、硬碳、硅基材料、锡基材料和钛酸锂中的一种或多种。硅基材料可包括单质硅、硅氧化物、硅碳复合物、硅氮复合物和硅合金材料中的一种或多种。锡基材料可包括单质锡、锡氧化物和锡合金材料中的一种或多种。本申请并不限定于这些材料，还可以使用其他可被用作负极活性材料的传统公知的材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
在一些实施例中，负极膜层还可选地包括负极导电剂。本申请对负极导电剂的种类没有特别的限制，作为示例，负极导电剂可包括超导碳、导电石墨、乙炔黑、碳黑、科琴黑、碳点、碳纳米管、石墨烯和碳纳米纤维中的一种或多种。
在一些实施例中，负极膜层还可选地包括负极粘结剂。本申请对负极粘结剂的种类没有特别的限制，作为示例，负极粘结剂可包括丁苯橡胶(SBR)、水溶性不饱和树脂SR-1B、水性丙烯酸类树脂(例如，聚丙烯酸PAA、聚甲基丙烯酸PMAA、聚丙烯酸钠PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)和羧甲基壳聚糖(CMCS)中的一种或多种。
在一些实施例中，负极膜层还可选地包括其他助剂。作为示例，其他助剂可包括增稠剂，例如，羧甲基纤维素钠(CMC)、PTC热敏电阻材料等。
负极膜层通常是将负极浆料涂布在负极集流体上，经干燥、冷压而成的。负极浆料通常是将负极活性材料、可选的负极导电剂、可选地负极粘结剂、其他可选的助剂分散于溶剂中并搅拌均匀而形成的。溶剂可以是N-甲基吡咯烷酮(NMP)或去离子水，但不限于此。
负极极片并不排除除了负极膜层之外的其他附加功能层。例如，在一些实施例中，负极极片还可包括夹在负极集流体和负极膜层之间、设置于负极集流体表面的导电底涂层(例如由导电剂和粘结剂组成)；在一些实施例中，负极极片还可包括覆盖在负极膜层表面的保护层。
在一些实施例中，负极极片可包括负极集流体以及设置在负极集流体至少一个表面上的第一金属层，第一金属层中的金属元素可包括锂元素。
在一些实施例中，第一金属层中的金属材料可包括锂单质、锂合金中的一种或多种。
锂合金可以是金属锂与其他金属元素或非金属元素形成的合金。作为示例，锂合金中的其他金属元素可包括锡、锌、铝、镁、银、金、镓、铟、铂中的一种或多种元素， 锂合金中的非金属元素可包括硼、碳、硅中的一种或多种元素。
在一些实施例中，负极极片可包括负极集流体、不包括第一金属层，以组装形成无负极金属电池单体。
在一些实施例中，负极极片还可以采用锂单质或锂合金的片材(或箔材)。
[电解质]
本申请实施例提供的电池单体包括电解质。电解质在正极极片和负极极片之间起到传导离子的作用。本申请对电解质的种类没有具体的限制，可根据需求进行选择。例如，电解质可包括固态电解质、凝胶态电解质及液态电解质(即电解液)中的一种或多种。
在一些实施例中，电解质采用电解液，电解液包括电解质盐和溶剂。
电解质盐的种类不受具体的限制，可根据实际需求进行选择。在一些实施例中，作为示例，电解质盐可包括六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、高氯酸锂(LiClO4)、六氟砷酸锂(LiAsF6)、双氟磺酰亚胺锂(LiFSI)、双三氟甲磺酰亚胺锂(LiTFSI)、三氟甲磺酸锂(LiTFS)、二氟草酸硼酸锂(LiDFOB)、二草酸硼酸锂(LiBOB)、二氟磷酸锂(LiPO2F2)、二氟二草酸磷酸锂(LiDFOP)和四氟草酸磷酸锂(LiTFOP)中的一种或多种。
溶剂的种类不受具体的限制，可根据实际需求进行选择。在一些实施例中，溶剂可以包括酯类溶剂、砜类溶剂、醚类溶剂中的一种或多种。作为示例，溶剂可包括但不限于碳酸乙烯酯(EC)、碳酸亚丙酯(PC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸亚丁酯(BC)、氟代碳酸亚乙酯(FEC)、甲酸甲酯(MF)、乙酸甲酯(MA)、乙酸乙酯(EA)、乙酸丙酯(PA)、丙酸甲酯(MP)、丙酸乙酯(EP)、丙酸丙酯(PP)、丁酸甲酯(MB)、丁酸乙酯(EB)、1,4-丁内酯(GBL)、环丁砜(SF)、二甲砜(MSM)、甲乙砜(EMS)、二乙砜(ESE)、四氢呋喃(THF)、2-甲基四氢呋喃、1,3-二氧戊烷、4-甲基-1,3-二氧环戊烷、二甲氧基甲烷、二乙氧基甲烷、二丙氧基甲烷、1,2-二甲氧基乙烷、1,2-二甲氧基丙烷、1,2-二乙氧基乙烷、乙二醇甲基乙基醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚中的一种或多种。
在一些实施例中，电解液中还可选地包括添加剂。例如，添加剂可包括负极成膜添加剂，也可包括正极成膜添加剂，还可包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温性能的添加剂、改善电池低温功率性能的添加剂等。
[隔离膜]
本申请实施例提供的电池单体还可包括隔离膜。隔离膜可设置在正极极片和负极极片之间，主要起到防止内部短路的作用。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构膜。
在一些实施例中，隔离膜的材质可包括玻璃纤维、无纺布、聚乙烯、聚丙烯、聚偏二氟乙烯、聚酰亚胺中的一种或多种。隔离膜可以是单层薄膜，也可以是多层复合薄膜。隔离膜为多层复合薄膜时，各层的材料相同或不同。
本申请实施例提供的电池单体的制备方法是公知的。在一些实施例中，可将正极极片、隔离膜、负极极片和电解液组装形成电池单体。作为示例，可将正极极片、隔离膜、 负极极片经卷绕工艺和/或叠片工艺形成电极组件，将电极组件置于外包装中，烘干后注入上述电解液，经过真空封装、静置、化成、整形等工序，得到电池单体。多个电池单体还可以进一步经由串联或并联或混联组成电池模块。多个电池模块还可以经由串联或并联或混联形成电池包。在一些实施例中，多个电池单体还可以直接组成电池包。
本申请实施例还提供一种用电装置，用电装置包括本申请实施例提供的电池。电池可以用作用电装置的电源，也可以用作用电装置的能量存储单元。用电装置可以但不限于是移动设备(例如手机、平板电脑、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等。
用电装置可以根据其使用需求来选择电池的具体类型，例如可以选择电池单体、电池模块或电池包。
图6是作为一个示例的用电装置的示意图。该用电装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置对高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的用电装置可以是手机、平板电脑、笔记本电脑等。该用电装置通常要求轻薄化，可以采用电池单体作为电源。
实施例
下述实施例更具体地描述了本申请公开的内容，这些实施例仅仅用于阐述性说明，因为在本申请公开内容的范围内进行各种修改和变化对本领域技术人员来说是明显的。除非另有声明，以下实施例中所报道的所有份、百分比和比值都是基于重量计，而且实施例中使用的所有试剂都可商购获得或是按照常规方法进行合成获得，并且可直接使用而无需进一步处理，以及实施例中使用的仪器均可商购获得。
实施例1-1
(1)聚噻吩导电聚合物的制备
在氮气环境中，将1mol甲氧基噻吩、1.5mol正戊醇、2g无水硫酸氢钠依次加入反应器中，于110℃加热搅拌3h，经减压蒸馏后得到3-戊氧基噻吩。
将3-戊氧基噻吩(第一单体化合物)、3-噻吩甲醇(第三单体化合物)按照摩尔比3:4干混，共取约10g溶于100mL氯仿中，之后在氮气环境中加入500mL浓度为0.2mol/L的无水FeCl3的氯仿溶液中，在25℃下聚合反应约24h；随后向反应体系中加入甲醇使聚合产物沉淀，将获得的沉淀物在乙醇中抽提48h，经干燥得到中间体。
在氮气环境中，将约5g分子量为1000的聚乙二醇单甲醚(MPEG)与约1g二苯基甲烷二异氰酸酯溶于100mL N,N-二甲基甲酰胺中，于70℃搅拌约2h，随后加入含有约6g上述中间体的N,N-二甲基甲酰胺溶液50mL，并继续在氮气环境中于70℃搅拌约6h；将反应产物用乙醇抽提24h，经真空干燥，得到聚噻吩导电聚合物。聚噻吩导电聚合物包括表1所示的第一结构单元、第三结构单元和第四结构单元，并且n1:n2:(n3+n4)为3:0:4，n4/(n3+n4)为0.12。聚噻吩导电聚合物的数均分子量如表1所示。采用核磁共振波谱法(NMR)可以得到聚噻吩导电聚合物中不同结构单元的相对含量。
(2)正极极片的制备
将体积分布粒径Dv50为7μm的正极活性材料磷酸铁锂与聚偏氟乙烯、聚噻吩导电聚 合物、导电炭黑(Super P)按照重量比96:2:1.5:0.5加入NMP中均匀分散，得到正极浆料；将正极浆料双面涂布于13μm厚的1060铝箔上，随后烘干蒸发溶剂，再经过冷压得到面密度为0.6g/1540.25mm2、压实密度为2.5g/cm3的初始正极极片。
将上述初始正极极片的其中一个正极膜层按停留时间为0.5s在5个激光器组成的总功率为2000W的495nm蓝光下进行连续照射，激光器与初始正极极片的垂直距离为10cm；接着采用相同方式处理初始正极极片的另一个正极膜层，结束后得到正极极片。
(3)负极极片的制备
将负极活性材料人造石墨、导电剂导电碳黑(Super P)、增稠剂羧甲基纤维素、粘结剂丁苯橡胶(SBR)按照重量比96:1:1:2在适量的溶剂去离子水中充分搅拌混合，形成均匀的负极浆料；将负极浆料双面涂布于6μm厚的铜箔上，经干燥、冷压后，得到负极极片。
(4)电解液的制备
将碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照按体积比1:1:1进行混合得到有机溶剂，接着将充分干燥的LiPF6溶解于上述有机溶剂中，配制成浓度为1mol/L的电解液。
(5)隔离膜的制备
采用多孔聚乙烯膜作为隔离膜。
(6)电池的制备
将正极极片、隔离膜、负极极片按顺序堆叠并卷绕，得到电极组件；将电极组件置于外包装中，干燥后注入电解液，经过真空封装、静置、化成等工序，得到电池。
实施例1-2
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物和正极极片制备工艺不同。
(1)聚噻吩导电聚合物的制备
在氮气环境中，将1mol甲氧基噻吩、1.5mol正丁醇、2g无水硫酸氢钠、100mL甲苯依次加入反应器中，于80℃加热搅拌4h，经减压蒸馏后得3-丁氧基噻吩。
将3-丁氧基噻吩(第一单体化合物)、3-噻吩甲醇(第三单体化合物)按照摩尔比3:4干混，共取约10g溶于100mL氯仿中，之后在氮气环境中加入500mL浓度0.2mol/L的无水FeCl3的氯仿溶液中，在25℃下聚合反应约48h；随后向反应体系中加入甲醇使聚合产物沉淀，将获得的沉淀物在乙醇中抽提36h，经干燥得到中间体。
在氮气环境中，将约4g分子量为400的聚乙二醇单甲醚(MPEG)与约1g二苯基甲烷二异氰酸酯溶于100mL N,N-二甲基甲酰胺中，于70℃搅拌3h，随后加入含有约7g上述中间体的N,N-二甲基甲酰胺溶液50mL，并继续在氮气环境中于70℃搅拌约5h；将反应产物用乙醇抽提48h，经真空干燥，得到聚噻吩导电聚合物。聚噻吩导电聚合物包括表1所示的第一结构单元、第三结构单元和第四结构单元，并且n1:n2:(n3+n4)为3:0:4，n4/(n3+n4)为0.12。聚噻吩导电聚合物的数均分子量如表1所示。
(2)正极极片的制备
将体积分布粒径Dv50为5μm的正极活性材料磷酸铁锂与聚偏氟乙烯、聚噻吩导电聚合物、导电炭黑(Super P)按照重量比97:1:1.3:0.7加入NMP中均匀分散，得到正极浆 料；将正极浆料双面涂布于15μm厚的1070铝箔上，随后烘干蒸发溶剂，再经过冷压得到面密度为0.65g/1540.25mm2、压实密度为2.45g/cm3的初始正极极片。
将上述初始正极极片的其中一个正极膜层按停留时间为0.3s在4个激光器组成的总功率为2500w的455nm蓝光下进行连续照射，激光器与初始正极极片的垂直距离为5cm；接着采用相同方式处理初始正极极片的另一个正极膜层，结束后得到正极极片。
实施例1-3
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物的过程中，使用3-噻吩乙醇替代3-噻吩甲醇。聚噻吩导电聚合物包括表1所示的第一结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表1所示。
实施例1-4
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物的过程中，使用六亚甲基二异氰酸酯替代二苯基甲烷二异氰酸酯。
聚噻吩导电聚合物包括表1所示的第一结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表1所示。
实施例1-5
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物的过程中，使用二环己基甲烷二异氰酸酯替代二苯基甲烷二异氰酸酯。
聚噻吩导电聚合物包括表1所示的第一结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量分别如表1所示。
实施例1-6
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物时，未加入聚乙二醇单甲醚(MPEG)和二苯基甲烷二异氰酸酯。制备的聚噻吩导电聚合物包括表1所示的第一结构单元和第三结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表1所示。
实施例1-7
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
(1)聚噻吩导电聚合物的制备
在氮气环境中，将1mol甲氧基噻吩、1.5mol乳酸甲酯、2g无水硫酸氢钠、100mL甲苯依次加入反应体系中于85℃加热搅拌3.5h，经减压蒸馏后得2-(噻吩-3-氧基)丙酸甲酯。
将3-戊氧基噻吩(第一单体化合物)、2-(噻吩-3-氧基)丙酸甲酯(第二单体化合物的前体化合物)、3-噻吩甲醇(第三单体化合物)按照摩尔比5:0.5:4.5干混，共取约10g溶 于100mL氯仿中，之后在氮气环境中加入500mL浓度为0.2mol/L的无水FeCl3的氯仿溶液中，在25℃下聚合反应约72h；随后向反应体系中加入甲醇使聚合产物沉淀，将获得的沉淀物在乙醇中抽提36h，经干燥得到中间体。
取5g中间体分散于水中，加入NaOH调节pH至8.5，并持续搅拌约6h；随后干燥得到聚噻吩导电聚合物。
聚噻吩导电聚合物包括表1所示的第一结构单元、第二结构单元和第三结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表1所示。
实施例1-8
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
(1)聚噻吩导电聚合物的制备
将3-戊氧基噻吩(第一单体化合物)、2-(噻吩-3-氧基)丙酸甲酯(第二单体化合物的前体化合物)、3-噻吩甲醇(第三单体化合物)按照摩尔比5:1:4.5干混，共取约10g溶于100mL氯仿中，之后在氮气环境中加入500mL浓度为0.2mol/L的无水FeCl3的氯仿溶液中，在25℃下聚合反应约96h；随后向反应体系中加入甲醇使聚合产物沉淀，将获得的沉淀物在乙醇中抽提36h，经干燥得到第一中间体。
在氮气环境中，将5g分子量为1000的聚乙二醇单甲醚(MPEG)与1g二苯基甲烷二异氰酸酯溶于100mL N,N-二甲基甲酰胺中，于70℃搅拌约2h，随后加入含有6g上述中间体的N,N-二甲基甲酰胺溶液50mL，并继续在氮气环境中于70℃搅拌约6h；将反应产物用乙醇抽提24h，经真空干燥，得到第二中间体。
将5g第二中间体分散于水中，加入NaOH调节pH至8.5，并持续搅拌6h；随后干燥得到聚噻吩导电聚合物。
聚噻吩导电聚合物包括表1所示的第一结构单元、第二结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表1所示。
实施例1-9至1-12
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物的数均分子量不同，具体详见表3。
实施例1-13至1-17
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物中各结构单元的含量以及数均分子量不同，具体详见表3。
实施例1-18至1-21
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物中各结构单元的含量以及数均分子量不同，具体详见表3。
在制备上述各实施例的聚噻吩导电聚合物时，可以根据本领域已知的方法调节单体的种类及浓度、氧化剂FeCl3的浓度、反应温度以及反应时间等参数中的一者或者多者，以获得不同的数均分子量。
对比例1-1
电池的制备方法与实施例1-1类似，不同之处在于正极极片的制备工艺不同。
将体积分布粒径Dv50为7μm的正极活性材料磷酸铁锂与聚偏氟乙烯、导电炭黑 (Super P)按照重量比96:2:2加入NMP中均匀分散，得到正极浆料；将正极浆料双面涂布于13μm厚的1060铝箔上，随后烘干蒸发溶剂，再经过冷压得到面密度为0.6g/1540.25mm2、压实密度为2.5g/cm3的正极极片。
对比例1-2
电池的制备方法与实施例1-1类似，不同之处在于正极极片的制备工艺不同。
将体积分布粒径Dv50为7μm的正极活性材料磷酸铁锂与聚偏氟乙烯、均聚聚噻吩(单体为噻吩，数均分子量在15000-20000之间)、导电炭黑(Super P)按照重量比96:2:1.3:0.7加入NMP中均匀分散，得到正极浆料；将正极浆料双面涂布于13μm厚的1060铝箔上，随后烘干蒸发溶剂，再经过冷压得到面密度为0.6g/1540.25mm2、压实密度为2.5g/cm3的初始正极极片。
将上述初始正极极片的其中一个正极膜层按停留时间为0.5s在5个激光器组成的总功率为2000W的495nm蓝光下进行连续照射，激光器与初始正极极片的垂直距离为10cm；接着采用相同方式处理初始正极极片的另一个正极膜层，结束后得到正极极片。
测试部分
(1)正极极片的电阻测试
将冷压后的正极极片裁成5cm×5cm，之后放置于电阻测试仪的两电极之间，测试正极极片的电阻值。电阻测试仪可以采用元能科技BER2500。测试温度为25℃。
(2)正极极片的粘结力测试
将正极极片用N-甲基吡咯烷酮洗去其中一面的正极膜层并烘干，然后将单面涂布的正极极片裁切为20mm×100mm的测试试样，备用；将测试试样用双面胶粘接需要测试的那一面，并用压辊压实，使双面胶与测试试样完全贴合；双面胶的另外一面粘贴于不锈钢表面，将测试试样的一端反向弯曲，弯曲角度为180°；采用高铁拉力机测试，将不锈钢一端固定于拉力机下方夹具，测试试样弯曲末端固定于上方夹具，调整测试试样角度，保证上下端位于垂直位置，然后以50mm/min的速度拉伸测试试样，直到从测试试样全部从基板剥离，记录过程中的位移和作用力，以受力平衡时的力作为正极极片的粘结力。
(3)正极极片的孔隙率测试
将正极极片裁切为14mm直径的圆形极片，数量为20片，记录下正极极片重量、厚度，计算得到体积密度。将圆形极片装入真密度孔隙率测试仪的样品杯中，利用氦气置换，并结合阿基米德定律与玻尔定律得到正极极片的真体积，进而计算出正极极片的真密度。正极极片的孔隙率＝(1-体积密度/真密度)。
(4)正极活性材料的克容量测试
将正极极片用N-甲基吡咯烷酮洗去其中一面的正极膜层并烘干，冲切成直径为14mm的单面圆形极片并称重；同时称重对应的正极集流体在直径为14mm圆片下的重量，得到正极膜层的重量，然后计算出正极活性材料的质量。
将2032扣式电池配套负极壳、泡沫镍、16mm直径锂片、18mm直径Celgard2325隔离膜、0.1g 1mol·L-1LiPF6的EC:DMC:EMC(质量比1:1:1)电解液、14mm直径单面圆形极片、2032扣式电池配套正极壳组装成2032型扣式电池。
将组装完成的扣式电池静置12h后进行测试。正极活性材料的质量乘以理论克容量即 为电池容量，记为C。将扣式电池以0.1C的电流充电至上限截止电压，再以0.1C的电流放电至上限截止电压。用扣式电池的放电容量除以正极活性材料的质量即得到正极活性材料的克容量。
(5)电池的直流内阻(DCR)测试
在25℃下，将各实施例和对比例制备的电池以0.33C恒流充电至满充状态(100％SOC)，然后以0.33C恒流放电至0.5Cn(Cn表示电池容量)以将电池调节至50％SOC；将电池静置30分钟，静置结束后的电压记为V1；之后将电池以3C的电流(记为I)放电30秒，放电截止电压记为V2。电池的直流内阻DCR＝(V1-V2)/I，V1表示静置结束电压，V2表示放电截止电压，I表示放电电流。
(6)电池的倍率性能测试
在25℃下，将各实施例和对比例制备的电池以0.33C恒流充电至3.65V，之后继续恒压充电至电流为0.05C，静置5分钟后，再将电池以0.33C恒流放电至2.5V，获得电池0.33C倍率下的放电容量；将电池静置30分钟后，以0.33C恒流充电至3.65V，之后恒压充电至电流为0.05C，静置5分钟后，再将电池以3C恒流放电至2.5V，获得电池3C倍率下的放电容量。以电池3C倍率下的放电容量与电池0.33C倍率下的放电容量的比值表示电池的倍率性能。该比值越大，电池的倍率性能越好。
实施例1-1至1-21和对比例1-1至1-2的测试结果示出在表2和表3中。
由表1至表3可知，本申请实施例提供的正极极片经过蓝光照射后，具有电阻小、粘结力高、孔隙率高、克容量高的特点，应用于电池中，可以降低电池内阻并提升电池的倍率性能。图7是实施例1-1和对比例1-1的电池在不同倍率下的放电曲线。由图7可知，实施例1-1制备的电池在3C倍率下具有更高的放电容量保持率。
实施例1-1至1-21的正极极片中的正极导电剂包括官能团化的聚噻吩导电聚合物，其对蓝光波长的吸收率更高，蓝光照射时加热效率更高，由此可以更好地改善正极极片中的正极粘结剂的分布，从而可以提升正极极片的粘结力和内聚力，并还可以降低正极电阻；蓝光照射过程中还可以释放应力，从而有利于形成孔隙率较高的正极膜层，进而可以提升正极极片的电解液浸润性。
由对比例1-2的测试结果还可知，正极导电剂包括均聚聚噻吩时，由于缺少红移官能团，此时正极极片的最大吸收峰对应的波长不在蓝光波长区间内，由此导致蓝光照射吸收率不高，进而对正极极片和电池的改善效果不明显。


实施例2-1
电池的制备方法与实施例1-1类似，不同之处在于聚噻吩导电聚合物和正极极片制备工艺不同。
(1)聚噻吩导电聚合物的制备
在氮气环境中，将1mol甲氧基噻吩、1.5mol乙醇酸乙酯、2g无水硫酸氢钠、100mL甲苯依次加入反应体系中于90℃加热搅拌3h，经减压蒸馏后得噻吩-3-氧基乙酸乙酯。
将3-戊氧基噻吩(第一单体化合物)、噻吩-3-氧基乙酸乙酯(第二单体化合物的前体化合物)、3-噻吩甲醇(第三单体化合物)按照摩尔比15:20:45干混，共取约10g溶于100mL氯仿中，之后在氮气环境中加入500mL浓度为0.2mol/L的无水FeCl3的氯仿溶液中，在25℃下聚合反应约48h；随后向反应体系中加入甲醇使聚合产物沉淀，将获得的沉淀物在乙醇中抽提36h，经干燥得到第一中间体。
在氮气环境中，将约8g分子量为6000的聚乙二醇单甲醚与约2g二苯基甲烷二异氰酸酯溶于100mL N,N-二甲基甲酰胺中，于70℃搅拌3h，随后加入含有约7g上述第一中间体的N,N-二甲基甲酰胺溶液50mL，并继续在氮气环境中于70℃搅拌约5h；将反应产物用乙醇抽提36h，经真空干燥，得到第二中间体。
取5g第二中间体分散于水中，加入NaOH调节pH至8.5，并持续搅拌约6h；随后干燥得到中和后的聚噻吩导电聚合物。聚噻吩导电聚合物包括表4所示的第一结构单元、第二结构单元、第三结构单元和第四结构单元，并且n1:n2:(n3+n4)为15:20:45，n4/(n3+n4)为0.05。聚噻吩导电聚合物的数均分子量如表4所示。
(2)正极极片的制备
将体积分布粒径Dv50为7μm的正极活性材料磷酸铁锂与羧甲基纤维素钠、聚噻吩导电聚合物、导电炭黑(Super P)按照重量比96:2:1.3:0.7加入去离子水中均匀分散，得到正极浆料；将正极浆料双面涂布于20μm厚的1070铝箔上，随后烘干蒸发溶剂，再经过冷压得到面密度为0.7g/1540.25mm2、压实密度为2.4g/cm3的初始正极极片。
将上述初始正极极片的其中一个正极膜层按停留时间0.25s在10个激光器组成的总功率为2500w的485nm蓝光下进行连续照射，激光器与初始正极极片的垂直距离为15cm；接着采用相同方式处理初始正极极片的另一个正极膜层，结束后得到正极极片。
实施例2-2
电池的制备方法与实施例2-1类似，不同之处在于聚噻吩导电聚合物和正极极片制备工艺不同。
将3-戊氧基噻吩(第一单体化合物)、2-(噻吩-3-氧基)丙酸甲酯(第二单体化合物的前体化合物)、3-噻吩甲醇(第三单体化合物)按照摩尔比15:20:45干混，共取约10g溶于100mL氯仿中，之后在氮气环境中加入500mL浓度为0.2mol/L的无水FeCl3的氯仿溶液中，在25℃下聚合反应约24h；随后向反应体系中加入甲醇使聚合产物沉淀，将获得的沉淀物在乙醇中抽提48h，经干燥得到第一中间体。
在氮气环境中，将约6.5g分子量为500的聚乙二醇单甲醚与约1.5g二苯基甲烷二异氰酸酯溶于100mL N,N-二甲基甲酰胺中，于70℃搅拌3h，随后加入含有约7g上述第一中间体的N,N-二甲基甲酰胺溶液50mL，并继续在氮气环境中于70℃搅拌约6h；将反应产物用乙醇抽提48h，经真空干燥，得到第二中间体。
取5.5g第二中间体分散于水中，加入LiOH调节pH至7.5，并持续搅拌约12h；随后干燥得到聚噻吩导电聚合物。聚噻吩导电聚合物包括表4所示的第一结构单元、第二结构单元、第三结构单元和第四结构单元，并且n1:n2:(n3+n4)为15:20:45，n4/(n3+n4)为0.05。聚噻吩导电聚合物的数均分子量如表4所示。
(2)正极极片的制备
将体积分布粒径Dv50为5μm的正极活性材料磷酸铁锂与海藻酸钠、聚噻吩导电聚合物、导电炭黑(Super P)按照重量比96.5:1.5:1.4:0.6加入去离子水中均匀分散，得到正极浆料；将正极浆料双面涂布于20μm厚的1070铝箔上，随后烘干蒸发溶剂，再经过冷压得到面密度为0.7g/1540.25mm2、压实密度为2.4g/cm3的初始正极极片。
将上述初始正极极片的其中一个正极膜层按停留时间0.2s在8个激光器组成的总功率为1500w的505nm蓝光下进行连续照射，激光器与初始正极极片的垂直距离为7.5cm；接着采用相同方式处理初始正极极片的另一个正极膜层，结束后得到正极极片。
实施例2-3
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物的过程中，使用2-(噻吩-3-氧基)乳酸甲酯替代2-(噻吩-3-氧基)丙酸甲酯。聚噻吩导电聚合物包括表4所示的第一结构单元、第二结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表4所示。
实施例2-4
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物的过程中，使用3-噻吩乙醇替代3-噻吩甲醇。聚噻吩导电聚合物包括表4所示的第一结构单元、第二结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表4所示。
实施例2-5
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物的过程中，使用六亚甲基二异氰酸酯替代二苯基甲烷二异氰酸酯。聚噻吩导电聚合物包括表4所示的第一结构单元、第二结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表4所示。
实施例2-6
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物的过程中，使用二环己基甲烷二异氰酸酯替代二苯基甲烷二异氰酸酯。聚噻吩导电聚合物包括表4所示的第一结构单元、第二结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表4所示。
实施例2-7
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物时，未加入第二单体化合物，也未加入聚乙二醇单甲醚(MPEG)和二苯基甲烷二异氰酸酯。制备的聚噻吩导电聚合物包括表4所示的第一结构单元和第三结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表4所示。
实施例2-8
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物时，未加入第二单体化合物。制备的聚噻吩导电聚合物包括表4所示的第一结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表4所示。
实施例2-9
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物的结构和制备工艺不同。
在制备聚噻吩导电聚合物时，未加入第二单体化合物。制备的聚噻吩导电聚合物包括表4所示的第一结构单元、第三结构单元和第四结构单元，并且各结构单元的含量以及聚噻吩导电聚合物的数均分子量如表4所示。
实施例2-10至1-14
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物的数均分子量不同，具体详见表6。
实施例2-15至1-18
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物中各结构单元的含量以及数均分子量不同，具体详见表6。
实施例2-19至1-22
电池的制备方法与实施例2-2类似，不同之处在于聚噻吩导电聚合物中各结构单元的含量以及数均分子量不同，具体详见表6。
实施例2-23
电池的制备方法与实施例2-2类似，不同之处在于第二中间体用NaOH调节pH至7.5。
在制备上述各实施例的聚噻吩导电聚合物时，可以根据本领域已知的方法调节单体的种类及浓度、氧化剂FeCl3的浓度、反应温度以及反应时间等参数中的一者或者多者，以获得不同的数均分子量。
对比例2-1
电池的制备方法与实施例2-2类似，不同之处在于正极极片的制备工艺不同。
将体积分布粒径Dv50为5μm的正极活性材料磷酸铁锂与海藻酸钠、导电炭黑(Super P)按照重量比96.5:1.5:2加入去离子水中均匀分散，得到正极浆料；将正极浆料双面涂布于20μm厚的1070铝箔上，随后烘干蒸发溶剂，再经过冷压得到面密度为 0.7g/1540.25mm2、压实密度为2.4g/cm3的正极极片。
对比例2-2
电池的制备方法与实施例2-2类似，不同之处在于正极极片的制备工艺不同。
将体积分布粒径Dv50为5μm的正极活性材料磷酸铁锂与海藻酸钠、均聚聚噻吩(单体为噻吩，数均分子量在15000-20000之间)、导电炭黑(Super P)按照重量比96.5:1.5:1.4:0.6加入去离子水中均匀分散，得到正极浆料；将正极浆料双面涂布于20μm厚的1070铝箔上，随后烘干蒸发溶剂，再经过冷压得到面密度为0.7g/1540.25mm2、压实密度为2.4g/cm3的初始正极极片。
将上述初始正极极片的其中一个正极膜层按停留时间0.2s在8个激光器组成的总功率为1500w的505nm蓝光下进行连续照射，激光器与初始正极极片的垂直距离为7.5cm；接着采用相同方式处理初始正极极片的另一个正极膜层，结束后得到正极极片。
实施例2-1至2-23和对比例2-1至2-2的测试方法与实施例1-1至1-21相同。结果示出在表5和表6中。
由表4至表6可知，本申请实施例提供的正极极片经过蓝光照射后，具有电阻小、粘结力高、孔隙率高、克容量高的特点，应用于电池中，可以降低电池内阻并提升电池的倍率性能。
实施例2-1至2-23的正极极片中的正极导电剂包括官能团化的聚噻吩导电聚合物，其对蓝光波长的吸收率更高，蓝光照射时加热效率更高，由此可以更好地改善正极极片中的正极粘结剂的分布，从而可以提升正极极片的粘结力和内聚力，并还可以降低正极电阻；蓝光照射过程中还可以释放应力，从而有利于形成孔隙率较高的正极膜层，进而可以提升正极极片的电解液浸润性。
由对比例2-2的测试结果还可知，正极导电剂包括均聚聚噻吩时，由于缺少红移官能团，此时正极极片的最大吸收峰对应的波长不在蓝光波长区间内，由此导致蓝光照射吸收率不高，进而对正极极片和电池的改善效果不明显。
需要说明的是，本申请不限定于上述实施方式。上述实施方式仅为示例，在本申请的技术方案范围内具有与技术思想实质相同的构成、发挥相同作用效果的实施方式均包含在本申请的技术范围内。此外，在不脱离本申请主旨的范围内，对实施方式施加本领域技术人员能够想到的各种变形、将实施方式中的一部分构成要素加以组合而构筑的其它方式也包含在本申请的范围内。



Claims (21)

  1. 一种聚噻吩导电聚合物，包括：
    式(1)所示的第一结构单元；以及
    式(2)所示的第二结构单元、式(3)所示的第三结构单元和式(4)所示的第四结构单元中的至少一者，
    R11包括C1-C8烷基或C1-C8烷基烷氧基，R12包括氢原子或C1-C3烷基；
    R21包括C1-C5亚烷基，R22包括氢原子或C1-C3烷基，M包括一价金属；
    R31包括C1-C5亚烷基，R32包括氢原子或C1-C3烷基；
    R41包括C1-C5亚烷基，R42包括二异氰酸酯的残基，R43包括C2-C6亚烷基，R44包括C1-C3烷基，R45包括氢原子或C1-C3烷基，s≥1；
    n1＞0；
    n2≥0，n3≥0，n4≥0，且n2+n3+n4＞0。
  2. 根据权利要求1所述的聚噻吩导电聚合物，其中，所述聚噻吩导电聚合物的数均分子量为3000-45000，可选为5000-34000。
  3. 根据权利要求1或2所述的聚噻吩导电聚合物，其中，所述聚噻吩导电聚合物满足如下条件(1)至(13)中的至少一者：
    (1)R11包括C4-C6烷基或C4-C6烷基烷氧基；
    (2)R12包括氢原子；
    (3)R21包括C1-C3亚烷基；
    (4)R22包括氢原子；
    (5)M包括Li和/或Na；
    (6)R31包括C1-C3亚烷基；
    (7)R32包括氢原子；
    (8)R41包括C1-C3亚烷基；
    (9)R42包括Ra取代或未取代的C1-C6亚烷基、以及如下基团中的一种：

    #表示连接位置，Ra分别独立地包括C1-C3烷基，Rb分别独立地包括C1-C3烷基，p表示0-4的整数，q表示0-6的整数；
    (10)R43包括如下基团：
    (11)R44包括甲基；
    (12)R45包括氢原子；
    (13)s为3-140，可选为10-90。
  4. 根据权利要求1-3任一项所述的聚噻吩导电聚合物，其中，
    n2＞0，n3＝0，n4＝0；或者，
    n2＝0，n3＞0，n4＝0；或者，
    n2＝0，n3＞0，n4＞0；或者，
    n2＞0，n3＞0，n4＞0。
  5. 一种正极浆料，包括溶剂以及非溶剂组分，所述非溶剂组分包括正极活性材料、正极粘结剂以及正极导电剂，其中，所述正极导电剂包括权利要求1-4任一项所述的聚噻吩导电聚合物。
  6. 根据权利要求5所述的正极浆料，其中，所述溶剂非水溶剂，可选为包括包括N-甲基吡咯烷酮，所述正极粘结剂包括油性粘结剂，且0.35≤n1/(n1+n2+n3+n4)≤0.65；
    可选地，0.40≤n1/(n1+n2+n3+n4)≤0.60；和/或，
    可选地，所述正极粘结剂包括聚偏氟乙烯、聚酰亚胺、聚氨酯中的一种或多种。
  7. 根据权利要求6所述的正极浆料，其中，
    0≤n2/(n1+n2+n3+n4)≤0.25，可选地，0≤n2/(n1+n2+n3+n4)≤0.10；和/或，
    0.35≤(n3+n4)/(n1+n2+n3+n4)≤0.65，
    可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60；和/或，
    0≤n4/(n3+n4)≤0.20，可选地，0＜n4/(n3+n4)≤0.15。
  8. 根据权利要求5所述的正极浆料，其中，所述溶剂包括水，所述正极粘结剂包括水性粘结剂，且0.05≤n1/(n1+n2+n3+n4)≤0.25；
    可选地，0.08≤n1/(n1+n2+n3+n4)≤0.22；和/或，
    可选地，所述正极粘结剂包括羧甲基纤维素及其衍生物、海藻酸钠、聚丙烯酸及其衍生物、琼脂糖、明胶、卡拉胶、黄原胶、瓜尔胶、聚乙烯醇、聚丙烯酰胺中的一种或多种。
  9. 根据权利要求8所述的正极浆料，其中，
    0.15≤n2/(n1+n2+n3+n4)≤0.45，可选地，0.25≤n2/(n1+n2+n3+n4)≤0.40；和/或，
    0.30≤(n3+n4)/(n1+n2+n3+n4)≤0.80，
    可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60；和/或，
    0≤n4/(n3+n4)≤0.20，可选地，0.04≤n4/(n3+n4)≤0.15。
  10. 根据权利要求5-9任一项所述的正极浆料，其中，
    所述正极活性材料包括锂过渡金属氧化物、含锂磷酸盐、及其各自的改性化合物中的一种或多种；和/或，
    所述正极浆料还包括第二导电剂，所述第二导电剂包括超导碳、导电石墨、乙炔黑、碳黑、科琴黑、碳点、碳纳米管、石墨烯和碳纳米纤维中的一种或多种；和/或，
    所述非溶剂组分中的所述聚噻吩导电聚合物的含量为0.2-4％，可选为0.5-3％，基于所述非溶剂组分的总重量计。
  11. 一种正极极片，包括正极集流体以及设置在所述正极集流体至少一个表面上的正极膜层，其中，所述正极膜层包括正极活性材料、正极粘结剂以及正极导电剂，所述正极导电剂包括权利要求1-4任一项所述的聚噻吩导电聚合物。
  12. 根据权利要求11所述的正极极片，其中，所述正极粘结剂包括油性粘结剂，且0.35≤n1/(n1+n2+n3+n4)≤0.65；
    可选地，0.40≤n1/(n1+n2+n3+n4)≤0.60；和/或，
    可选地，所述正极粘结剂包括聚偏氟乙烯、聚酰亚胺、聚氨酯中的一种或多种。
  13. 根据权利要求12所述的正极极片，其中，
    0≤n2/(n1+n2+n3+n4)≤0.25，可选地，0≤n2/(n1+n2+n3+n4)≤0.10；和/或，
    0.35≤(n3+n4)/(n1+n2+n3+n4)≤0.65，
    可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60；和/或，
    0≤n4/(n3+n4)≤0.20，可选地，0＜n4/(n3+n4)≤0.15。
  14. 根据权利要求11所述的正极极片，其中，
    所述正极粘结剂包括水性粘结剂，且0.05≤n1/(n1+n2+n3+n4)≤0.25；
    可选地，0.08≤n1/(n1+n2+n3+n4)≤0.22；和/或，
    可选地，所述正极粘结剂包括羧甲基纤维素及其衍生物、海藻酸钠、聚丙烯酸及其衍生物、琼脂糖、明胶、卡拉胶、黄原胶、瓜尔胶、聚乙烯醇、聚丙烯酰胺中的一种或多种。
  15. 根据权利要求14所述的正极极片，其中，
    0.15≤n2/(n1+n2+n3+n4)≤0.45，可选地，0.25≤n2/(n1+n2+n3+n4)≤0.40；和/或，
    0.30≤(n3+n4)/(n1+n2+n3+n4)≤0.80，
    可选地，0.40≤(n3+n4)/(n1+n2+n3+n4)≤0.60；和/或，
    0≤n4/(n3+n4)≤0.20，可选地，0.04≤n4/(n3+n4)≤0.15。
  16. 根据权利要求11-15任一项所述的正极极片，其中，
    所述正极活性材料包括锂过渡金属氧化物、含锂磷酸盐、及其各自的改性化合物中的一种或多种；和/或，
    所述正极极片还包括第二导电剂，所述第二导电剂包括超导碳、导电石墨、乙炔黑、碳黑、科琴黑、碳点、碳纳米管、石墨烯和碳纳米纤维中的一种或多种；和/或，
    所述正极膜层中的所述聚噻吩导电聚合物的含量为0.2-4％，可选为0.5-3％，基于所述正极膜层的总重量计。
  17. 一种正极极片的制备方法，其中，包括如下步骤：
    将权利要求5-10任一项所述的正极浆料涂布在正极集流体至少一个表面上，干燥、辊压后获得初始正极极片；
    使用激光照射所获得的初始正极极片，结束后获得正极极片，所述激光波长为445-505nm。
  18. 根据权利要求17所述的制备方法，其中，
    激光发生方式为连续发射；和/或，
    激光器的数量为1-10，总功率为100-2500W；和/或，
    所述初始正极极片经过激光器光斑的时间为0.05-0.5s；和/或，
    激光器与所述初始正极极片的垂直距离为5-15cm。
  19. 一种电池单体，其中，包括权利要求11-16任一项所述的正极极片或通过权利要求17-18任一项所述的制备方法制备得到的正极极片。
  20. 一种电池，其中，包括权利要求19所述的电池单体。
  21. 一种用电装置，其中，包括权利要求20所述的电池。
PCT/CN2024/083548 2023-07-03 2024-03-25 聚噻吩导电聚合物、正极浆料、正极极片及其制备方法、电池单体、电池和用电装置 Ceased WO2025007595A1 (zh)

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