WO2025107768A1 - 叠片式电芯、方形锂电池及电池包 - Google Patents

叠片式电芯、方形锂电池及电池包 Download PDF

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Publication number
WO2025107768A1
WO2025107768A1 PCT/CN2024/113981 CN2024113981W WO2025107768A1 WO 2025107768 A1 WO2025107768 A1 WO 2025107768A1 CN 2024113981 W CN2024113981 W CN 2024113981W WO 2025107768 A1 WO2025107768 A1 WO 2025107768A1
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Prior art keywords
electrode sheet
positive electrode
lithium battery
square lithium
negative electrode
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Pending
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PCT/CN2024/113981
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English (en)
French (fr)
Inventor
夏阳
车丽媛
杨杰
王晓坤
吴婷婷
温圣耀
苑丁丁
何巍
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Eve Power Co Ltd
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Eve Power Co Ltd
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Publication date
Application filed by Eve Power Co Ltd filed Critical Eve Power Co Ltd
Priority to EP24853007.3A priority Critical patent/EP4583236A4/en
Publication of WO2025107768A1 publication Critical patent/WO2025107768A1/zh
Priority to US19/337,847 priority patent/US20260018754A1/en
Priority to MX2025014229A priority patent/MX2025014229A/es
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/54—Connection of several leads or tabs of plate-like electrode stacks, e.g. electrode pole straps or bridges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape of the leads or tabs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/538—Connection of several leads or tabs of wound or folded electrode stacks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application relates to the technical field of lithium batteries, and in particular to a laminated battery cell, a square lithium battery and a battery pack.
  • the size of the pole piece of a lithium battery will affect the performance of the lithium battery in actual applications.
  • the internal resistance of a lithium battery cell is not only related to the length of the pole piece, but also to the thickness of the pole piece.
  • the length and width of the pole piece are constant, the thicker the pole piece, the longer the lithium ion diffusion distance and the greater the internal resistance of the cell; conversely, under the premise that the length and width of the pole piece are constant, the thinner the pole piece, the smaller the internal resistance of the cell.
  • the pole piece is too thin, the energy density of the lithium battery will be reduced.
  • the present application provides a laminated battery cell, the laminated battery cell comprising a plurality of battery cell units stacked in sequence along a first direction, each of the battery cell units comprising a positive electrode sheet, a separator and a negative electrode sheet stacked in sequence, and a separator is arranged between two adjacent battery cell units, the first direction is perpendicular to a first surface of the positive electrode sheet close to the separator, the positive electrode sheet of each battery cell unit is provided with a sub-electrode ear, and the negative electrode sheet of each battery cell unit is provided with a sub-electrode ear; the sub-electrode ears of the positive electrode sheets of the plurality of battery cell units are connected in sequence to form a positive electrode ear, and the sub-electrode ears of the negative electrode sheets of the plurality of battery cell units are connected in sequence to form a negative electrode ear; the ratio of the length of the positive electrode sheet to the thickness and the ratio of the length of the negative electrode sheet to the thickness are independently selected from 6.3 ⁇
  • the present application also provides a square lithium battery, the square lithium battery comprising one or more laminated cells, each of the laminated cells comprising a plurality of cell units stacked in sequence along a first direction, each of the cell units comprising a positive electrode sheet, a separator and a negative electrode sheet stacked in sequence, and a separator is arranged between two adjacent cell units, the first direction is perpendicular to the first surface of the positive electrode sheet close to the separator, the positive electrode sheet of each cell unit is provided with a sub-electrode ear, and the negative electrode sheet of each cell unit is provided with a sub-electrode ear; the sub-electrode ears of the positive electrode sheets of the plurality of cell units are connected in sequence to form a positive electrode ear, and the sub-electrode ears of the negative electrode sheets of the plurality of cell units are connected in sequence to form a negative electrode ear; the ratio of the length of the positive electrode sheet to the thickness and the ratio of the length of the negative electrode sheet to the thickness are
  • the present application also provides a battery pack, which includes a box and a plurality of square lithium batteries, wherein the box is formed with a storage space, and the plurality of square lithium batteries are sequentially arranged in the storage space;
  • the square lithium batteries include one or more laminated cells, each of the laminated cells includes a plurality of cell units sequentially stacked along a first direction, each of the cell units includes a positive electrode sheet, a separator and a negative electrode sheet sequentially stacked, and a separator is provided between two adjacent cell units, the first direction is perpendicular to a first surface of the positive electrode sheet close to the separator, the positive electrode sheet of each cell unit is provided with a sub-electrode ear, and the negative electrode sheet of each cell unit is provided with a sub-electrode ear; the sub-electrode ears of the positive electrode sheets of the plurality of cell units are sequentially connected to form a positive electrode ear, and the sub-electrode ears of the negative electrode sheets of the plurality of
  • the laminated battery cell provided in the present application ensures that the laminated battery cell has an acceptable internal resistance by controlling the sizes of the positive electrode sheet and the negative electrode sheet.
  • the square lithium battery provided in the present application includes one or more of the above-mentioned stacked battery cells, which improves the actual capacity, energy density, rate performance and cycle stability of the square lithium battery, and is beneficial to improving the safety of the square lithium battery.
  • the battery pack provided in the present application includes a box body and a plurality of the above-mentioned square lithium batteries.
  • the plurality of square lithium batteries are arranged in sequence in the accommodating space of the box body, thereby improving the internal space utilization and battery life of the battery pack.
  • FIG1 is a schematic diagram of the structure of a laminated battery cell provided by some implementations of the present application.
  • FIG. 2 is a schematic diagram of the structure of a positive electrode sheet provided by some implementations of the present application.
  • FIG3 is a schematic diagram of the structure of a square lithium battery provided by some implementations of the present application.
  • FIG4 is a schematic diagram of the structure of a battery pack provided by some implementations of the present application.
  • 1 battery pack, 10: square lithium battery, 20: box, 30: cover, 40: buffer, 101: laminated battery cell, 102: shell, 103: positive electrode column, 104: negative electrode column, 105: connecting plate, 201: accommodating space, 202: box wall, 1011: battery cell unit, 1012: positive electrode ear, 1013: negative electrode ear, 10111: positive electrode sheet, 10112: diaphragm, 10113: negative electrode sheet, 101110: sub-electrode ear, 101111: first side, 101112: positive electrode current collector, 101113: positive electrode active material layer.
  • each embodiment of the present application may be in the form of a range; it should be understood that the description in the form of a range is for convenience and brevity and should not be understood as a rigid limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values within the range.
  • the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the numbered ranges, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range.
  • a numerical range is indicated in this article, it is meant to include any cited numbers (fractions or integers) within the indicated range.
  • multiple refers to two (times) or more than two (times), for example, it can be two (times), three (times), four (times), five (times), six (times), etc.
  • the technical solution of "A, and/or, B, and/or, C, and/or, D” includes any one of A, B, C, and D (that is, the technical solution connected by "logical or"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the combination of four items of A, B, C, and D (that is, the technical solution connected by "logical and").
  • solid content refers to the ratio of the mass of solid matter in the slurry to the total mass of the slurry.
  • the laminated battery cell 101 includes a plurality of battery cell units 1011 sequentially stacked along a first direction X1, each battery cell unit 1011 includes a positive electrode sheet 10111, a separator 10112 and a negative electrode sheet 10113 sequentially stacked, and a separator 10112 is provided between two adjacent battery cell units 1011, and the first direction X1 is perpendicular to the first surface 1011 of the positive electrode sheet 10111 close to the separator 10112.
  • the positive electrode sheet 10111 of each battery cell unit 1011 is provided with a sub-electrode ear 101110 (positive electrode sheet sub-electrode ear), and the negative electrode sheet 10113 of each battery cell unit 1011 is provided with a sub-electrode ear 101110 (negative electrode sheet sub-electrode ear).
  • the sub-electrode ears 101110 of the positive electrode sheets 10111 of multiple battery cells 1011 are connected in sequence to form a positive electrode ear 1012, and the sub-electrode ears 101110 of the negative electrode sheets 10113 of multiple battery cells 1011 are connected in sequence to form a negative electrode ear 1013.
  • the surface of the electrode sheet located at the outermost layer of the laminated battery cell 101 is also provided with a diaphragm 10112.
  • the length of the positive electrode sheet 10111 and the length of the negative electrode sheet 10113 are independently selected from 135 mm to 165 mm, for example, they can be 135 mm to 140 mm, 135 mm to 145 mm, 135 mm to 150 mm, 135 mm to 155 mm, 135 mm to 160 mm, 145 mm to 150 mm, 145 mm to 155 mm, 145 mm to 160 mm, 145 mm to 165 mm, 150 mm to 155 mm, 150 mm to 160 mm, 150 mm to 165 mm, 155 mm to 160 mm, 155 mm to 165 mm, or 160 mm to 165 mm, examples are 135 mm, 140 mm, 145 mm, 151 mm, 155 mm, 160 mm, 165 mm or a value between any two of the foregoing values.
  • the width of the positive electrode sheet 10111 and the width of the negative electrode sheet 10113 are independently selected from 135 mm to 165 mm, for example, they can be 135 mm to 140 mm, 135 mm to 145 mm, 135 mm to 150 mm, 135 mm to 155 mm, 135 mm to 160 mm, 145 mm to 150 mm, 145 mm to 155 mm, 145 mm to 160 mm, 145 mm to 165 mm, 150 mm to 155 mm, 150 mm to 160 mm, 150 mm to 165 mm, 155 mm to 160 mm, 155 mm to 165 mm, or 160 mm to 165 mm, examples are 135 mm, 140 mm, 145 mm, 148 mm, 155 mm, 160 mm, 165 mm or a value between any two of the foregoing values.
  • the ratio of the length to the thickness of the positive electrode sheet 10111 and the ratio of the length to the thickness of the negative electrode sheet 10113 are independently selected from 6.3 ⁇ 10 2 to 9.4 ⁇ 10 2 , for example, 6.3 ⁇ 10 2 to 8.0 ⁇ 10 2 , 6.3 ⁇ 10 2 to 7.5 ⁇ 10 2 , 7.7 ⁇ 10 2 to 8.5 ⁇ 10 2 , or 8.0 ⁇ 10 2 to 8.5 ⁇ 10 2 , exemplified by 6.3 ⁇ 10 2 , 6.5 ⁇ 10 2 , 7.0 ⁇ 10 2 , 7.4 ⁇ 10 2 , 7.7 ⁇ 10 2 , 8.0 ⁇ 10 2 , 8.5 ⁇ 10 2 , 9.0 ⁇ 10 2 , 9.4 ⁇ 10 2 , or a value between any two of the foregoing values.
  • the ratio of the width to thickness of the positive electrode sheet 10111 and the ratio of the width to thickness of the negative electrode sheet 10113 are independently selected from 6.3 ⁇ 10 2 to 9.4 ⁇ 10 2 , for example, 6.3 ⁇ 10 2 , 6.5 ⁇ 10 2 , 7.0 ⁇ 10 2 , 7.4 ⁇ 10 2 , 7.7 ⁇ 10 2 , 8.0 ⁇ 10 2 , 8.5 ⁇ 10 2 , 9.0 ⁇ 10 2 , 9.4 ⁇ 10 2 or a value between any two of the foregoing values.
  • the positive electrode sheet 10111 includes a positive electrode current collector 101112 and a positive electrode active material layer 101113, and the positive electrode active material layer 101113 is disposed on the surface of the positive electrode current collector 101112.
  • the thickness of the positive electrode current collector 101112 is a constant value and all other structures and compositions in the lithium battery except the positive electrode sheet 10111 remain unchanged, if the thickness of the positive electrode active material layer 101113 is thicker, the internal resistance of the battery cell is greater, and the corresponding ion diffusion distance in the lithium battery is longer, and the impedance of the lithium battery is greater; if the thickness of the positive electrode active material layer 101113 is thinner, the internal resistance of the battery cell is smaller, and the battery capacity of the corresponding lithium battery is reduced.
  • the number of positive electrode sheets 10111 needs to be increased, resulting in an increase in the amount of foil used for the positive electrode current collector 101112, thereby increasing the weight and manufacturing cost of the lithium battery, and causing a decrease in the energy density of the lithium battery.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer, and the negative electrode active material layer is arranged on the surface of the negative electrode current collector; under the premise that the thickness of the negative electrode current collector is a constant value and all other structures and compositions in the lithium battery except the negative electrode sheet remain unchanged, if the thickness of the negative electrode active material layer is thicker, the internal resistance of the battery cell is greater, and the corresponding impedance of the lithium battery is greater; if the thickness of the negative electrode active material layer is thinner, the internal resistance of the battery cell is smaller, and the battery capacity of the corresponding lithium battery is reduced. If the battery capacity is to be increased to a preset value, the number of negative electrode sheets needs to be increased, thereby increasing the weight and manufacturing cost of the lithium battery, and causing the energy density of the lithium battery to decrease.
  • the stacked battery cell 101 of the embodiment of the present application on the premise that the length of the positive electrode sheet 10111 and the length of the negative electrode sheet 10113 are respectively controlled within the range of 135 mm to 165 mm, and the width of the positive electrode sheet 10111 and the width of the negative electrode sheet 10113 are respectively controlled within the range of 135 mm to 165 mm, within the range of the ratio of the length to the thickness of the aforementioned electrode sheets and the range of the ratio of the width to the thickness, it can be ensured that the stacked battery cell 101 has an acceptable internal resistance and that the lithium battery including the stacked battery cell 101 has a good energy density.
  • the thickness of the positive electrode sheet 10111 and the thickness of the negative electrode sheet 10113 are independently selected from 180 ⁇ m to 215 ⁇ m, for example, it can be 180 ⁇ m to 190 ⁇ m, 180 ⁇ m to 200 ⁇ m, 180 ⁇ m to 210 ⁇ m, 190 ⁇ m to 200 ⁇ m, 190 ⁇ m to 210 ⁇ m, 190 ⁇ m to 215 ⁇ m, 200 ⁇ m to 210 ⁇ m or 210 ⁇ m to 215 ⁇ m, and examples are 180 ⁇ m, 185 ⁇ m, 190 ⁇ m, 193 ⁇ m, 197 ⁇ m, 200 ⁇ m, 205 ⁇ m, 210 ⁇ m, 215 ⁇ m or a value between any two of the aforementioned values.
  • the material of the positive electrode active material layer 101113 includes a lithium iron manganese phosphate material
  • the general chemical formula of the lithium iron manganese phosphate material is Li a Mn x Fe y M z (PO 4 ) b , where a, x, y, z and b respectively represent the molar amounts of the corresponding elements, the sum of x, y and z is c, and M is selected from one or more of Mg, Ca, Sr, Co, Ti, Zr, Mo, V, Nb, Nd, Y, Ni, Sc, Cr, Cu, Zn, Be, La and Al.
  • LiaMnxFeyMz ( PO4 ) b 0.10 ⁇ x ⁇ 0.70
  • x is, for example, 0.10 , 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, or a value between any two of the foregoing values.
  • x the higher the x, the higher the molar content of Mn in the corresponding lithium manganese iron phosphate material, and the higher the average voltage of the positive electrode sheet 10111. If x is greater than 0.7, the diffusion of lithium ions may be weakened during actual application, resulting in a decrease in the conductivity of the positive electrode sheet 10111, thereby reducing the power of the lithium battery including the laminated battery cell 101.
  • 0.10 ⁇ x ⁇ 0.68, 0.26 ⁇ x ⁇ 0.68, or 0.4 ⁇ x ⁇ 0.68 In order to increase the average voltage of the positive electrode sheet 10111 and ensure that the positive electrode sheet 10111 has good electrical conductivity, thereby improving the electrochemical performance of the stacked battery cell 101, in some embodiments of the present application, 0.10 ⁇ x ⁇ 0.68, 0.26 ⁇ x ⁇ 0.68, or 0.4 ⁇ x ⁇ 0.68.
  • the ratio of a to c, a/c, is 1.01 ⁇ a/c ⁇ 1.10, and a/c can be, for example, 1.01-1.03, 1.01-1.05, 1.01-1.08, 1.015-1.035, 1.035-1.05, 1.035-1.08, 1.035-1.10 , 1.05-1.08, or 1.05-1.10, exemplified by 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, or a value between any two of the foregoing values.
  • a/c is lower than 1.01 (i.e., the Li content is low), the actual gram capacity of the lithium iron manganese phosphate material will decrease. If a/c is greater than 1.10 (i.e., the Li content is high), then when the lithium iron manganese phosphate material is wetted by water, the residual alkali content on the surface of the lithium iron manganese phosphate material will increase. If the residual alkali content is too high, the lithium battery will "swell", resulting in a decrease in the cycle performance of the square lithium battery.
  • the ratio of a to b is a/b, 0.95 ⁇ a/b ⁇ 1.10, for example, it can be 0.95 ⁇ a/b ⁇ 1.00, 0.95 ⁇ a/b ⁇ 1.03, 0.95 ⁇ a/b ⁇ 1.05, 0.95 ⁇ a/b ⁇ 1.08, 1.00 ⁇ a/b ⁇ 1.03, 1.00 ⁇ a/b ⁇ 1.08, 1.00 ⁇ a/b ⁇ 1.10 or 1.03 ⁇ a/b ⁇ 1.10, examples of a/b are 0.96, 0.98, 1.00, 1.01, 1.02, 1.03, 1.05, 1.08, 1.10 or any two values between the foregoing value; the ratio of c to b is c/b, 0.90 ⁇ c/b ⁇ 1.1
  • the element type of M is one of the key factors affecting the performance of lithium iron manganese phosphate materials.
  • M is selected from Mg to improve the sintering property of lithium iron manganese phosphate materials, which is beneficial to improve the rate performance of lithium batteries containing lithium iron manganese phosphate materials.
  • the molar amount of M will also affect the performance of lithium iron manganese phosphate materials.
  • 0.01 ⁇ z ⁇ 0.12 In order to ensure that M has a good modification effect on lithium iron manganese phosphate materials and avoid poor electrochemical performance due to excessive molar amount of M, 0.01 ⁇ z ⁇ 0.12, for example, it can be 0.01 ⁇ z ⁇ 0.03, 0.01 ⁇ z ⁇ 0.05, 0.01 ⁇ z ⁇ 0.08, 0.01 ⁇ z ⁇ 0.10, 0.05 ⁇ z ⁇ 0.08, or 0.05 ⁇ z ⁇ 0.12, and examples are 0.01, 0.02, 0.03, 0.05, 0.08, 0.10, 0.12 or a value between any two of the aforementioned values.
  • a coating layer is provided on the surface of the lithium iron manganese phosphate material, and the material of the coating layer includes a carbon material, and the mass of the carbon material accounts for 0.5% to 3% of the sum of the mass of the carbon material and the lithium iron manganese phosphate material.
  • the coating layer also has a protective effect on the lithium iron manganese phosphate material, and can improve the dissolution of Fe and Mn caused by the infiltration of the lithium iron manganese phosphate material by water (such as electrolyte), and the thickness of the coating layer is, for example, 3 nm to 5 nm.
  • the present application also provides a method for preparing a lithium iron manganese phosphate material, which can be used to prepare any of the lithium iron manganese phosphate materials mentioned above, comprising the following steps:
  • S1 providing a first slurry including a lithium source, a manganese source, an iron source, a phosphorus source and an M source;
  • each raw material can be selected according to conventional methods in the art.
  • the lithium source can be one or more of lithium oxide, lithium hydroxide and lithium salt
  • lithium oxide includes but is not limited to Li2O
  • anions generated by ionization of lithium salt include but are not limited to one or more of oxalate ion, carbonate ion, sulfate ion, nitrate ion, acetate ion, halogen ion, phosphate ion and dihydrogen phosphate ion
  • examples of lithium salt include one or more of lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium dihydrogen phosphate, lithium phosphate and lithium oxalate.
  • the manganese source can be one or more of manganese oxide, manganese hydroxide and manganese salt.
  • the manganese oxide includes but is not limited to one or more of manganese monoxide, manganese dioxide and manganese tetraoxide.
  • the anions generated by the ionization of the manganese salt include but are not limited to one or more of oxalate ion, carbonate ion, sulfate ion, nitrate ion, acetate ion, halide ion and phosphate ion.
  • Examples of manganese sources are one or more of manganese carbonate, manganese phosphate, manganese oxalate, manganese nitrate, manganese acetate, manganese sulfate and manganese chloride.
  • the iron source is one or more of iron oxide, iron hydroxide and iron salt.
  • the iron oxide includes but is not limited to one or more of ferroferric oxide, ferrous oxide and ferrous oxide.
  • the anions generated by the ionization of the iron salt include but are not limited to one or more of oxalate ion, carbonate ion, sulfate ion, nitrate ion, acetate ion, halide ion and phosphate ion.
  • iron salts are one or more of ferrous sulfate, ferric chloride, ferrous phosphate, ferrous phosphate, ferrous pyrophosphate, ferric pyrophosphate, ferric nitrate, ferric acetate, ferric citrate, ferrous oxalate and ferrous chloride.
  • the phosphorus source includes, but is not limited to, one or more of phosphoric acid and phosphorus-containing metal salts, wherein the phosphorus-containing metal salt includes, but is not limited to, one or more of ammonium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate and iron phosphate.
  • the M source is, for example, a compound containing one or more of Mg, Ca, Sr, Co, Ti, Zr, Mo, V, Nb, Nd, Y, Ni, Sc, Cr, Cu, Zn, Be, La and Al, and the compound may be an oxide, hydroxide or metal salt compound.
  • the titanium source may be one or more of titanium oxide, metatitanic acid, tetrabutyl titanate, titanium hydroxide and titanium salt
  • the titanium oxide includes but is not limited to TiO 2
  • the anions generated by the ionization of the titanium salt include but are not limited to one or more of oxalate ions, carbonate ions, sulfate ions, nitrate ions, acetate ions, halogen ions and phosphate ions
  • the titanium salt is exemplified by one or more of titanium sulfate, titanium nitrate and titanium chloride
  • the cobalt source includes but is not limited to one or more of cobalt tetroxide, cobalt nitrate, cobaltous oxide, cobalt acetate and cobalt phosphate
  • taking the M source as a nickel source as an example the nickel source includes but is not
  • the first slurry also includes a carbon source, which can be one or more of an inorganic carbon source and an organic carbon source, wherein the inorganic carbon source includes but is not limited to one or more of graphene, carbon nanotubes and graphite, and the organic carbon source includes but is not limited to one or more of glucose, sucrose, lactose, starch, organic acid, vitamins and phenolic resins, and the carbon source can act as a reducing agent to effectively improve the oxidation of Mn 2+ and Fe 2+ in the sintering process.
  • a carbon source which can be one or more of an inorganic carbon source and an organic carbon source, wherein the inorganic carbon source includes but is not limited to one or more of graphene, carbon nanotubes and graphite, and the organic carbon source includes but is not limited to one or more of glucose, sucrose, lactose, starch, organic acid, vitamins and phenolic resins, and the carbon source can act as a reducing agent to effectively improve the oxidation of Mn
  • the solvent of the first slurry may be, for example, water and/or an organic solvent, wherein water is preferably deionized water, and the selectable organic solvent includes, but is not limited to, alcohol compounds having 1 to 10 carbon atoms, such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-methyl-2-propanol, n-pentanol, 2-methyl-1-butanol, and 2,2-dimethyl-1-1-propanol.
  • the solvent of the first slurry is preferably water, because compared with organic solvents, water has a lower cost and has the advantages of being environmentally friendly, having low equipment requirements, and being highly safe.
  • the solid content of the first slurry is 10% to 40%, for example, it can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or a value between any two of the foregoing values, so that the first slurry has a suitable viscosity for subsequent grinding processing.
  • the purpose of the grinding treatment is to refine the raw materials, improve the uniformity of the subsequent spray drying and sintering treatments, and help control the particle size of crystal growth during the sintering process.
  • the grinding treatment method includes, but is not limited to, one or more of sand milling, ball milling, mechanical stirring milling, and air flow milling.
  • the process conditions of the grinding treatment can refer to the conventional conditions used in the art, for example: grinding treatment is carried out by sand milling, and sand milling is carried out at a speed of 200 r/min to 1000 r/min for 1 h to 6 h.
  • step S3 the process conditions of the spray drying treatment can refer to the conventional conditions used in the art.
  • step S4 the purpose of the sintering treatment is to make all raw materials undergo a solid phase reaction to generate lithium iron manganese phosphate.
  • the sintering treatment needs to be carried out in an environment isolated from oxygen, such as in an inert gas atmosphere, and the inert gas includes but is not limited to one or more of nitrogen, argon, helium, argon, neon, krypton and xenon; when the surface of the obtained lithium iron manganese phosphate material does not have a carbon coating layer, the sintering treatment can be carried out in an atmosphere containing oxygen or in an inert gas atmosphere; the equipment used for the sintering treatment includes but is not limited to a muffle furnace, a tubular furnace, a rotary kiln, a roller kiln or a push plate kiln.
  • the method for preparing the lithium iron manganese phosphate material also includes the step of: crushing the sintered material obtained after the sintering treatment, and then passing the crushed material through a 150-200 mesh sieve for screening, and the material passing through the sieve is the lithium iron manganese phosphate material.
  • the material of the laminated battery 101 also includes a positive electrode binder and a positive electrode conductor.
  • the material of the positive electrode collector 101112, the positive electrode binder and the positive electrode conductor can be conventional materials in the art, for example: the material of the positive electrode collector 101112 includes but is not limited to aluminum foil or composite aluminum foil; the positive electrode binder includes but is not limited to one or more of vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and polytetrafluoroethylene; the positive electrode conductor includes but is not limited to one or more of carbon black, graphite and graphene.
  • the preparation method of the positive electrode sheet 10111 includes, for example, the steps of: mixing a lithium manganese iron phosphate material, a positive electrode conductive agent, a positive electrode binder and a first solvent to obtain a first mixture; then, coating the first mixture on the positive electrode collector 101112, and then sequentially performing a drying process and a rolling process to obtain the positive electrode sheet 10111.
  • the first mixture can also be cast on a separate carrier to form a film layer, and then the film layer is separated from the carrier, and then the film layer is stacked on the surface of the positive electrode collector 101112.
  • the first solvent includes but is not limited to N-methylpyrrolidone, dimethylformamide or ethylene glycol dimethyl ether.
  • the materials of the negative electrode active material layer include a negative electrode active material, a negative electrode binder and a negative electrode conductor.
  • the negative electrode current collector material, negative electrode active material, negative electrode binder and negative electrode conductive agent may be conventional materials in the art, for example: the negative electrode current collector material includes but is not limited to copper foil, composite copper foil or copper mesh; the negative electrode active material includes but is not limited to lithium element, metals that can be alloyed with lithium, semi-metals, transition metal oxides, non-transition metal oxides and carbon materials, the metals or semi-metals that can be alloyed with lithium include but are not limited to Si, Sn, Al, Ge, Pb, Bi, Sb, Si- Y1 alloy ( Y1 is alkali metal, alkaline earth metal, 13-16 group element, transition metal, rare earth element, or a combination thereof, except Si), and Sn- Y2 alloy ( Y2 is alkali metal, alkaline earth metal, 13-16 group element, transition metal, rare earth element, or
  • the material of the diaphragm 10112 includes, but is not limited to, one or more of glass fiber, polyester, Teflon, polyethylene, polypropylene, and polytetrafluoroethylene.
  • the embodiment of the present application also provides a square lithium battery.
  • the square lithium battery 10 includes one or more laminated battery cells 101 as described above.
  • One or more laminated battery cells 101 constitute the battery cell of the square lithium battery 10 .
  • the ratio of the length to the width of the square lithium battery 10 is 1.00-1.13, for example, it can be 1.00-1.03, 1.00-1.05, 1.00-1.08, 1.00-1.12, 1.06-1.07, or 1.06-1.13, and examples are 1.00, 1.03, 1.05, 1.08, 1.10, 1.13 or a value between any two of the foregoing values.
  • the length of the square lithium battery is selected from 165 mm to 185 mm, for example, it can be 165 mm to 170 mm, 170 mm to 180 mm, 174 mm to 180 mm, 175 mm to 176 mm, or 180 mm to 185 mm, and examples are 165 mm, 170 mm, 175 mm, 180 mm, 185 mm or a value between any two of the aforementioned values; and/or, the width of the square lithium battery is selected from 155 mm to 170 mm, for example, it can be 160 mm to 170 mm, 160 mm to 165 mm, 164 mm to 165 mm, or 165 mm to 170 mm, and examples are 155 mm, 160 mm, 165 mm, 170 mm or a value between any two of the aforementioned values.
  • the square lithium battery 10 when used as a battery element of a vehicle battery pack, especially a commercial vehicle (including but not limited to trucks, logistics vehicles or engineering vehicles), the length and width size design of the square lithium battery 10 is conducive to improving the internal space utilization and endurance of the battery pack, and can take into account the structural strength and heat dissipation effect of the square lithium battery 10.
  • the ratio of the length to the thickness of the square lithium battery 10 is 3.4 ⁇ 10 3 to 4.5 ⁇ 10 3 , for example, it can be 3.4 ⁇ 10 3 to 3.8 ⁇ 10 3 , 3.4 ⁇ 10 3 to 4.0 ⁇ 10 3 , 3.4 ⁇ 10 3 to 4.3 ⁇ 10 3 , 3.8 ⁇ 10 3 to 4.0 ⁇ 10 3 , 4.0 ⁇ 10 3 to 4.1 ⁇ 10 3 , or 4.0 ⁇ 10 3 to 4.5 ⁇ 10 3 , examples are 3.4 ⁇ 10 3 , 3.8 ⁇ 10 3 , 4.0 ⁇ 10 3 , 4.5 ⁇ 10 3 or a value between any two of the foregoing values; the ratio of the width to the thickness of the square lithium battery 10 is 3.3 ⁇ 10 2 to 4.3 ⁇ 10 2 , for example, it can be 3.3 ⁇ 10 3 3 to 3.5 ⁇ 10 3 , 3.3 ⁇ 10 3 to 4.0 ⁇ 10 3 , 3.3 ⁇ 10 3 to 4.3 ⁇ 10 3 , 3.7 ⁇ 10 3 to 3.8 ⁇ 10 3 , 3.8 ⁇ 10
  • the thickness of the square lithium battery 10 is selected from 35 mm to 55 mm, for example, it can be 35 mm to 40 mm, 35 mm to 45 mm, 35 mm to 50 mm, 40 mm to 45 mm, 40 mm to 50 mm, 43 mm to 44 mm or 45 mm to 50 mm, examples are 35 mm, 40 mm, 43 mm, 44 mm, 45 mm, 50 mm, 55 mm or a value between any two of the foregoing values.
  • the length-to-thickness ratio design and the width-to-thickness ratio design of the aforementioned square lithium battery 10 can optimize the spatial distribution of the energy of the square lithium battery 10 in the battery pack; in addition, the thickness dimension design of the aforementioned square lithium battery 10 can ensure that there is sufficient heat dissipation area between any two adjacent square lithium batteries 10 in the battery pack, thereby ensuring the heat dissipation effect, and reducing the volume share of a single square lithium battery 10, which is conducive to the compact arrangement of multiple square lithium batteries 10 in the battery pack.
  • the square lithium battery 10 also includes other conventional structural parts.
  • the square lithium battery 10 also includes a shell 102, a positive electrode column 103 and a negative electrode column 104.
  • the positive electrode column 103 and the negative electrode column 104 are respectively arranged on the surface of the shell 102, and the laminated battery 101 is arranged in the shell 102.
  • the material of the shell 102 is, for example, aluminum.
  • the positive electrode ear 1012 and the positive electrode column 103 are welded together through the connecting piece 105 by a spot welding process to form the positive electrode of the square lithium battery 10
  • the negative electrode ear 1013 and the negative electrode column 104 are welded together through the connecting piece 105 by a spot welding process to form the negative electrode of the square lithium battery 10.
  • the square lithium battery 10 also includes an electrolyte, and the electrolyte soaks the laminated battery core 101.
  • the electrolyte can be a conventional component in the art, for example: the electrolyte includes a lithium salt and an organic solvent, wherein the organic solvent is selected from two or more of ethylene carbonate, propylene carbonate , dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene sulfite, ethyl acetate, diethyl sulfite, and 1,3 -propane sultone; the lithium salt is selected from LiPF6, LiClO4, LiBF4, LiSbF6, LiAsF6, LiCF3SO3 , Li ( CF3SO2 ) 2N , LiC4F9SO3 , LiAlO2 , LiAlCl4 , LiODFB, LiTFSI, LiFSI, LiCl, LiI, and LiN( CxF2x +1SO2
  • the AC internal resistance of the square lithium battery 10 (composed of one or more stacked battery cells 101) at 25°C is 0.2 m ⁇ to 0.5 m ⁇ , and/or the energy density of the square lithium battery is 190 Wh/kg to 220 Wh/kg, and/or the capacity of the square lithium battery is 175 Ah to 250 Ah, and/or the voltage of the square lithium battery is 2.5 V to 4.2 V.
  • the embodiment of the present application also provides a battery pack, as shown in FIG. 4 , the battery pack 100 includes a box body 20 and a plurality of square lithium batteries 10 as described above, the box body 20 forms a receiving space 201 , and the plurality of square lithium batteries 10 are arranged in sequence in the receiving space 201 .
  • the battery pack 100 also includes other conventional structural parts.
  • the battery pack 100 also includes a cover 30 and a buffer 40.
  • the cover 30 is used to cover the internal space of the box 20.
  • the buffer 40 is arranged in the box 20 and is located at the box wall 202 of the box 20. It is understandable that the battery pack 100 may also include components such as a battery management system and a cooling device.
  • An embodiment of the present application also provides an application of any laminated battery cell as described above, or any square lithium battery as described above, or any battery pack as described above in a vehicle, wherein the battery cell, or square lithium battery, or battery pack serves as a power source for the vehicle.
  • the vehicle is selected from a truck, a logistics vehicle or an engineering vehicle.
  • the square lithium battery 10 includes a laminated battery cell 101, a shell 102, a positive electrode column 103 and a negative electrode column 104, wherein the laminated battery cell 101 is arranged in the shell 102, the material of the shell 102 is, for example, aluminum, and the positive electrode column 103 and the negative electrode column 104 are respectively arranged on the surface of the shell 102.
  • the stacked battery cell 101 includes 55 battery cell units 1011 stacked in sequence along a first direction X1, each battery cell unit 1011 includes a positive electrode sheet 10111, a separator 10112 and a negative electrode sheet 10113 stacked in sequence, the first direction X1 is perpendicular to the first surface 101111 of the positive electrode sheet 10111 close to the separator 10112, the sub-pole ears 101110 of the positive electrode sheets 10111 of all the battery cell units 1011 are connected in sequence to form the positive electrode ears 1012, and the sub-pole ears 101110 of the negative electrode sheets 10113 of all the battery cell units 1011 are connected in sequence to form the negative electrode ears 1013.
  • the positive electrode ear 1012 and the negative electrode ear 1013 are respectively located at the opening of the shell 102, the positive electrode ear 1012 and the positive electrode column 103 are welded together to form the positive electrode of the square lithium battery 10, and the negative electrode ear 1013 and the negative electrode column 104 are welded together to form the negative electrode of the square lithium battery 10.
  • the square lithium battery 10 also includes an electrolyte, and the electrolyte infiltrates the laminated battery 101.
  • the positive electrode sheet 10111 includes a positive electrode current collector 101112 and a positive electrode active material layer 101113.
  • the positive electrode active material layer 101113 is arranged on the surface of the positive electrode current collector 101112.
  • the material of the positive electrode current collector 101112 is carbon-coated aluminum foil (thickness is 12 ⁇ m).
  • the material of the positive electrode active material layer 101113 includes Li 0.96 Fe 0.3 Mn 0.6 Mg 0.04 PO 4 coated with carbon material. The average thickness of the coating layer is 3 nm, and the mass of the carbon material accounts for 1.5% of the total mass of the carbon material and Li 0.96 Fe 0.3 Mn 0.6 Mg 0.04 PO 4 .
  • the preparation method of the positive electrode sheet 10111 includes the following steps: weighing the above four raw materials according to the mass ratio of carbon material-coated Li 0.96 Fe 0.3 Mn 0.6 Mg 0.04 PO 4 : carbon black conductive (Super PLL): carbon nanotubes: polyvinylidene fluoride in a mass ratio of 97:0.4:0.5:2.1, and evenly mixing the above four raw materials with N-methylpyrrolidone to obtain a positive electrode slurry, wherein the solid content of the positive electrode slurry is 65%; then, coating the positive electrode slurry on an aluminum foil with a thickness of 12 ⁇ m (coated on both sides) by a coating machine, and then baking and curing at 120°C to form a positive electrode active material layer, and then cold pressing to a corresponding thickness by a roller press to obtain a positive electrode sheet.
  • the preparation method of carbon material coated Li 0.96 Fe 0.3 Mn 0.6 V 0.04 PO 4 comprises the following steps:
  • the particle size distribution range of the pre-burned material is 2 ⁇ m to 5 ⁇ m;
  • the burned material is subjected to air flow pulverization treatment and 150-mesh sieve screening treatment in sequence, and the material passing through the 150-mesh sieve is subjected to a single iron removal treatment process to obtain carbon material-coated Li 0.96 Fe 0.3 Mn 0.6 V 0.04 PO 4 .
  • the negative electrode sheet 10113 includes a negative electrode current collector and a negative electrode active material layer, wherein the negative electrode active material layer is disposed on the surface of the negative electrode current collector, wherein the material of the negative electrode current collector is aluminum foil (thickness of 12 ⁇ m), and the material of the negative electrode active material layer includes graphite.
  • the preparation method of the negative electrode sheet 10113 includes the steps of: weighing the above four raw materials according to the mass ratio of graphite: conductive carbon black (Super PLL): carboxymethyl cellulose: styrene-butadiene rubber of 97:0.7:1.25:1.05, uniformly mixing the above four raw materials with N-methylpyrrolidone to obtain a negative electrode slurry, wherein the solid content of the negative electrode slurry is 55%; then, coating the negative electrode slurry on an aluminum foil with a thickness of 8 ⁇ m (coated on both sides) by a coating machine, then baking and curing at 80°C to form a negative electrode active material layer, and then cold pressing to a corresponding thickness by a roller press to obtain a negative electrode sheet.
  • Super PLL conductive carbon black
  • the preparation method of the electrolyte includes the steps of: mixing ethylene carbonate (EC): diethyl carbonate (DEC): ethyl methyl carbonate (EMC) in a volume ratio of 4:3:3 to obtain a solvent, then adding LiPF6 and an additive to the solvent, and mixing them evenly to obtain an electrolyte, wherein the concentration of LiPF6 in the electrolyte is 1.0 mol/L, the mass of the additive accounts for 10% of the total mass of the electrolyte, the additive consists of vinylene carbonate, 1,3-propane sultone, fluoroethylene carbonate and cyclohexylbenzene, and the mass ratio of vinylene carbonate: 1,3-propane sultone: fluoroethylene carbonate: cyclohexylbenzene is 3:2:1:1.
  • the preparation method of the square lithium battery 10 includes the steps of: forming a battery unit 1011 by stacking a positive electrode sheet 10111, a PP separator 10112 with a thickness of 12 ⁇ m, and a negative electrode sheet 10113, forming a stacked battery 101 by stacking 55 battery units 1011, assembling two stacked battery cells 101 with an aluminum shell, and then injecting electrolyte, and then undergoing aging, formation, shaping, packaging and other processes to obtain a square lithium battery 10.
  • the dimensions of the positive electrode sheet 10111 and the negative electrode sheet 10113 are exactly the same (the dimensions of the positive electrode active material layer and the negative electrode active material layer are exactly the same).
  • the dimensions of the positive electrode sheet 10111, the negative electrode sheet 10113 and the square lithium battery 10 in this embodiment are shown in Table 1 below:
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the thickness of the positive electrode sheet and the negative electrode sheet are respectively replaced with "190 ⁇ m".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the thickness of the positive electrode sheet and the negative electrode sheet are respectively replaced with "180 ⁇ m".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the thickness of the positive electrode sheet and the negative electrode sheet are respectively replaced with "210 ⁇ m".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the thickness of the positive electrode sheet and the negative electrode sheet are respectively replaced with "215 ⁇ m".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the widths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "145 mm”.
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the widths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "155 mm”.
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the widths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "135 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the widths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "165 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the lengths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "145 mm”.
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the lengths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "155 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the lengths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "135 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the lengths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "165 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the difference of the square lithium battery in this embodiment is only that the length of the positive electrode sheet and the negative electrode sheet are respectively replaced with "145 mm", and the width of the positive electrode sheet and the negative electrode sheet are respectively replaced with "140 mm”.
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Example 1, the difference of the square lithium battery in this embodiment is only that the length of the positive electrode sheet and the negative electrode sheet are replaced with "150 mm” respectively, and the width of the positive electrode sheet and the negative electrode sheet are replaced with "140 mm” respectively.
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the difference of the square lithium battery in this embodiment is only that the length of the positive electrode sheet and the negative electrode sheet are respectively replaced with "155 mm", and the width of the positive electrode sheet and the negative electrode sheet are respectively replaced with "155 mm”.
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Example 1, the difference of the square lithium battery in this embodiment is only that the length of the positive electrode sheet and the negative electrode sheet are replaced with "165 mm” respectively, and the width of the positive electrode sheet and the negative electrode sheet are replaced with "135 mm” respectively.
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the difference of the square lithium battery in this embodiment is only that the thickness of the square lithium battery is replaced with "35 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the difference of the square lithium battery in this embodiment is only that the thickness of the square lithium battery is replaced with "55 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the difference of the square lithium battery in this embodiment is only that the thickness of the square lithium battery is replaced with "40 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the difference of the square lithium battery in this embodiment is only that the thickness of the square lithium battery is replaced with "50 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the width of the square lithium battery is replaced with "170 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the width of the square lithium battery is replaced with "155 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the length of the square lithium battery is replaced with "165 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that the length of the square lithium battery is replaced with "185 mm".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that “Li 0.96 Fe 0.3 Mn 0.6 Mg 0.04 PO 4 ” in the positive electrode active material layer 101113 is replaced by “Li 0.96 Fe 0.3 Mn 0.6 V 0.04 PO 4 ”.
  • the preparation method of Li 0.96 Fe 0.3 Mn 0.6 V 0.04 PO 4 comprises the steps of: replacing "1.6 kg of magnesium oxide” in step S1.1 with "3 kg of vanadium trioxide".
  • This embodiment provides a square lithium battery. Compared with the square lithium battery provided in Embodiment 1, the square lithium battery in this embodiment is different only in that “Li 0.96 Fe 0.3 Mn 0.6 Mg 0.04 PO 4 ” in the positive electrode active material layer 101113 is replaced by “Li 0.96 Fe 0.3 Mn 0.6 Mg 0.02 V 0.02 PO 4 ”.
  • the preparation method of Li 0.96 Fe 0.3 Mn 0.6 Mg 0.02 V 0.02 PO 4 comprises the steps of: replacing "1.6 kg of magnesium oxide” in step S1.1 with "0.8 kg of magnesium oxide and 1.5 kg of vanadium trioxide".
  • This comparative example provides a square lithium battery. Compared with the square lithium battery provided in Example 1, the difference of the square lithium battery in this comparative example is that the thickness of the positive electrode sheet and the negative electrode sheet are respectively replaced with "250 ⁇ m".
  • This comparative example provides a square lithium battery. Compared with the square lithium battery provided in Example 1, the square lithium battery in this comparative example is different only in that the widths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "110 mm".
  • This comparative example provides a square lithium battery. Compared with the square lithium battery provided in Example 1, the difference of the square lithium battery in this comparative example is only that the lengths of the positive electrode sheet and the negative electrode sheet are respectively replaced with "110 mm".
  • This comparative example provides a square lithium battery. Compared with the square lithium battery provided in Example 1, the square lithium battery in this comparative example is different only in that the width of the square lithium battery is replaced with "140 mm".
  • This comparative example provides a square lithium battery. Compared with the square lithium battery provided in Example 1, the square lithium battery in this comparative example is different only in that the length of the square lithium battery is replaced by "150 mm.
  • the square lithium batteries in Examples 1 to 26 and Comparative Examples 1 to 5 were respectively subjected to electrical performance tests and thermal runaway tests, wherein the electrical performance test method comprises the steps of: charging each square lithium battery to 4.2 V at 0.2C rate constant current and constant voltage at 25°C, wherein the constant voltage charging cutoff current is 0.02C, and then discharging at 0.2C constant current until the voltage reaches 2.5V, obtaining the first discharge capacity and first charge capacity at 25°C and 0.2C rate, and calculating the first charge and discharge efficiency of each square lithium battery at 25°C and 0.2C rate (ratio of first discharge capacity to first charge capacity ⁇ 100%).
  • the detection method of the thermal runaway test is carried out with reference to the thermal runaway test method in Appendix A of GB38032-2020.
  • Example 1 139.32 158.5 87.9 pass
  • Example 2 139.44 157.2 88.7 pass
  • Example 3 139.35 155.7 89.5 pass
  • Example 4 138.71 159.8 86.8 pass
  • Example 5 136.74 160.3 85.3 pass
  • Example 6 135.12 160.1 84.4 pass
  • Example 7 136.00 162.1 83.9 pass
  • Example 8 131.30 162.9 80.6 pass
  • Example 9 137.23 158.1 86.8 pass
  • Example 10 139.11 157.9 88.1 pass Embodiment 11 138.82 159.2 87.2 pass
  • Example 12 132.80 153.7 86.4 pass
  • Example 13 128.56 160.5 80.1 pass
  • Embodiment 14 137.43 157.6 87.2 pass
  • Embodiment 15 138.02 157.2 87.8 pass
  • Example 16 140.34 158.4 88.6 pass Embodiment 17 137.56 159.4 86.3 pass
  • Embodiment 18

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Abstract

本申请公开了一种叠片式电芯、方形锂电池及电池包，通过控制正极片和负极片的尺寸以确保叠片式电芯具有可接受的内阻，并且提升了包含叠片式电芯的方形锂电池的实际容量、能量密度、倍率性能和循环稳定性，以及有利于提高方形锂电池的安全性。

Description

叠片式电芯、方形锂电池及电池包
本申请要求在2023年11月21日提交中国专利局、申请号为202311566713.X的中国专利申请的优先权，以上申请的全部内容通过引用结合在本申请中。
技术领域
本申请涉及锂电池技术领域，具体涉及一种叠片式电芯、方形锂电池及电池包。
 背景技术
随着便携式电子设备、新能源汽车以及大规模储能市场的不断发展，对锂电池的需求也持续增长。锂电池的极片尺寸会影响实际应用过程中锂电池的性能发挥，例如：锂电池的电芯内阻不仅与极片的长度相关，而且与极片的厚度相关，在片的长度和宽度均为恒定值的前提下，极片越厚，则锂离子扩散距离越长，电芯内阻越大；反之，在极片的长度和宽度均为恒定值的前提下，极片越薄，则电芯内阻越小，但若极片太薄，则会导致锂电池的能量密度降低。
 发明概述
如何调控极片的尺寸以使锂电池兼顾较低的电芯内阻和较高的能量密度对锂电池的应用和发展具有重要意义。
本申请提供了一种叠片式电芯，所述叠片式电芯包括沿着第一方向依次层叠设置的多个电芯单元，每一所述电芯单元包括依次层叠设置的一正极片、一隔膜以及一负极片，并且相邻两个所述电芯单元之间设有一所述隔膜，所述第一方向垂直于所述正极片靠近所述隔膜的第一面，每一所述电芯单元的所述正极片设有子极耳，每一所述电芯单元的所述负极片设有子极耳；多个所述电芯单元的正极片的子极耳依次连接而形成正极耳，多个所述电芯单元的负极片的子极耳依次连接而形成负极耳；所述正极片的长度对厚度的比值以及所述负极片的长度对厚度的比值分别独立地选自6.3×10 2～9.4×10 2，所述正极片的宽度对厚度的比值以及所述负极片的宽度对厚度的比值分别独立地选自6.3×10 2～9.4×10 2。
本申请还提供了一种方形锂电池，所述方形锂电池包括一个或多个叠片式电芯，每一所述叠片式电芯包括沿着第一方向依次层叠设置的多个电芯单元，每一所述电芯单元包括依次层叠设置的一正极片、一隔膜以及一负极片，并且相邻两个所述电芯单元之间设有一所述隔膜，所述第一方向垂直于所述正极片靠近所述隔膜的第一面，每一所述电芯单元的所述正极片设有子极耳，每一所述电芯单元的所述负极片设有子极耳；多个所述电芯单元的正极片的子极耳依次连接而形成正极耳，多个所述电芯单元的负极片的子极耳依次连接而形成负极耳；所述正极片的长度对厚度的比值以及所述负极片的长度对厚度的比值分别独立地选自6.3×10 2～9.4×10 2，所述正极片的宽度对厚度的比值以及所述负极片的宽度对厚度的比值分别独立地选自6.3×10 2～9.4×10 2。
本申请还提供了一种电池包，所述电池包包括箱体以及多个方形锂电池，所述箱体形成有容纳空间，多个所述方形锂电池依序排列于所述容纳空间内；所述方形锂电池包括一个或多个叠片式电芯，每一所述叠片式电芯包括沿着第一方向依次层叠设置的多个电芯单元，每一所述电芯单元包括依次层叠设置的一正极片、一隔膜以及一负极片，并且相邻两个所述电芯单元之间设有一所述隔膜，所述第一方向垂直于所述正极片靠近所述隔膜的第一面，每一所述电芯单元的所述正极片设有子极耳，每一所述电芯单元的所述负极片设有子极耳；多个所述电芯单元的正极片的子极耳依次连接而形成正极耳，多个所述电芯单元的负极片的子极耳依次连接而形成负极耳；所述正极片的长度对厚度的比值以及所述负极片的长度对厚度的比值分别独立地选自6.3×10 2～9.4×10 2，所述正极片的宽度对厚度的比值以及所述负极片的宽度对厚度的比值分别独立地选自6.3×10 2～9.4×10 2。
有益效果
本申请提供的叠片式电芯，通过控制正极片和负极片的尺寸以确保叠片式电芯具有可接受的内阻。
本申请提供的方形锂电池包括一个或多个上述的叠片式电芯，提升了方形锂电池的实际容量、能量密度、倍率性能和循环稳定性，以及有利于提高方形锂电池的安全性。
本申请提供的电池包包括箱体以及多个上述的方形锂电池，多个方形锂电池依序排列于箱体的容纳空间内，提高了电池包的内部空间利用率以及续航能力。
 附图说明
图1是本申请的一些实现方式提供的一种叠片式电芯的结构示意图。
图2是本申请的一些实现方式提供的一种正极片的结构示意图。
图3是本申请的一些实现方式提供的一种方形锂电池的结构示意图。
图4本申请的一些实现方式提供的一种电池包的结构示意图。
附图标记如下：
1：电池包，10：方形锂电池，20：箱体，30：盖体，40：缓冲件，101：叠片式电芯，102：壳体，103：正极柱，104：负极柱，105：连接片，201：容纳空间，202：箱壁，1011：电芯单元，1012：正极耳，1013：负极耳， 10111：正极片，10112：隔膜，10113：负极片，101110：子极耳，101111：第一面，101112：正极集流体，101113：正极活性材料层。
 本发明的实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述。显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
除非另行定义，文中所使用的所有专业与科学用语与本领域技术人员所熟悉的意义相同，并且本申请实施例和对比例中所用的材料或试剂可商购获得。此外，任何与所记载内容相似或均等的方法及材料皆可应用于本申请中。文中较佳实施方法与材料仅作示范之用，但不能限制本申请的内容。
需说明的是，以下实施例的描述顺序不作为对实施例优选顺序的限定。本申请的每一实施例可以以一个范围的型式存在；应当理解，以一范围型式的描述是因为方便及简洁，不应理解为对本申请范围的硬性限制；因此，应当认为范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如，应当认为从1到6的范围描述已经具体公开子范围，例如从1到3，从1到4，从1到5，从2到4，从2到6，从3到6等，以及所数范围内的单一数字，例如1、2、3、4、5及6，此不管范围为何皆适用。另外，每当在本文中指出数值范围，是指包括所指范围内的任何引用的数字(分数或整数)。
在本申请的描述中，术语“包括”是指“包括但不限于”。
术语“多种”、“多次”或其类似表达指的是两种(次)或两种(次)以上，例如可以是两种(次)、三种(次)、四种(次)、五种(次)、六种(次)等。
术语“和/或”的选择范围包括两个或两个以上相关所列项目中任一个项目，也包括相关所列项目的任意的和所有的组合，任意的和所有的组合包括任意的两个相关所列项目、任意的更多个相关所列项目、或者全部相关所列项目的组合。比如，“A和/或B”包括A、B以及A+B三种并列方案。又比如，“A，及/或，B，及/或，C，及/或，D”的技术方案，包括A、B、C、D中任一项(也即均用“逻辑或”连接的技术方案)，也包括A、B、C、D的任意的和所有的组合，也即包括A、B、C、D中任两项或任三项的组合，还包括A、B、C、D的四项组合(也即均用“逻辑与”连接的技术方案)。
术语“固含量”是指浆料中固形物的质量占浆料的总质量的比例。
本申请实施例提供了一种叠片式电芯，如图1和图3所示，叠片式电芯101包括沿着第一方向X1依次层叠设置的多个电芯单元1011，每一电芯单元1011包括依次层叠设置的一正极片10111、一隔膜10112以及一负极片10113，并且相邻两个电芯单元1011之间设有一隔膜10112，第一方向X1垂直于正极片10111靠近隔膜10112的第一面101111，每一电芯单元1011的正极片10111设有子极耳101110(正极片子极耳)，每一电芯单元1011的负极片10113设有子极耳101110(负极片子极耳)，多个电芯单元1011的正极片10111的子极耳101110依次连接而形成正极耳1012，且多个电芯单元1011的负极片10113的子极耳101110依次连接而形成负极耳1013。需要说明的是，位于叠片式电芯101最外层的电极片的表面同样设有隔膜10112。
其中，正极片10111的长度和负极片10113的长度分别独立地选自135 mm～165 mm，例如可以是135 mm～140 nm、135 mm～145 mm、135 mm～150 mm、135 mm～155 mm、135 mm～160 mm、145 mm～150 mm、145 mm～155 mm、145 mm～160 mm、145 mm～165 mm、150 mm～155 mm、150 mm～160 mm、150 mm～165 mm、155 mm～160 mm、155 mm～165 mm、或160 mm～165 mm，示例为135 mm、140 nm、145 mm、151 mm、155 mm、160 mm、165 mm或前述任意两个数值之间的值。
正极片10111的宽度和负极片10113的宽度分别独立地选自135 mm～165 mm，例如可以是135 mm～140 nm、135 mm～145 mm、135 mm～150 mm、135 mm～155 mm、135 mm～160 mm、145 mm～150 mm、145 mm～155 mm、145 mm～160 mm、145 mm～165 mm、150 mm～155 mm、150 mm～160 mm、150 mm～165 mm、155 mm～160 mm、155 mm～165 mm、或160 mm～165 mm，示例为135 mm、140 nm、145 mm、148 mm、155 mm、160 mm、165 mm或前述任意两个数值之间的值。
正极片10111的长度对厚度的比值以及负极片10113的长度对厚度的比值分别独立地选自6.3×10 2～9.4×10 2，例如可以是6.3×10 2～8.0×10 2、6.3×10 2～7.5×10 2、7.7×10 2～8.5×10 2、或8.0×10 2～8.5×10 2，示例为6.3×10 2、6.5×10 2、7.0×10 2、7.4×10 2、7.7×10 2、8.0×10 2、8.5×10 2、9.0×10 2、9.4×10 2或前述任意两个数值之间的值。正极片10111的宽度对厚度的比值以及负极片10113的宽度对厚度的比值分别独立地选自6.3×10 2～9.4×10 2，例如可以是6.3×10 2、6.5×10 2、7.0×10 2、7.4×10 2、7.7×10 2、8.0×10 2、8.5×10 2、9.0×10 2、9.4×10 2或前述任意两个数值之间的值。
需要说明的是，如图2所示，正极片10111包括正极集流体101112和正极活性材料层101113，正极活性材料层101113设置于正极集流体101112的表面。在正极集流体101112的厚度为恒定值且锂电池中除正极片10111之外其他所有结构及组成不变的前提下，若正极活性材料层101113的厚度越厚，则电芯内阻越大，对应锂电池中离子扩散距离越长，锂电池的阻抗越大；若正极活性材料层101113的厚度越薄，则电芯内阻越小，对应锂电池的电池容量降低，若要提高电池容量至预设值，则需增加正极片10111的数量，导致正极集流体101112的箔材用量增加，从而提高了锂电池的重量以及制造成本，并且造成锂电池的能量密度降低。同理，负极片包括负极集流体和负极活性材料层，负极活性材料层设置于负极集流体的表面；在负极集流体的厚度为恒定值且锂电池中除负极片之外其他所有结构及组成不变的前提下，若负极活性材料层的厚度越厚，则电芯内阻越大，对应锂电池的阻抗越大；若负极活性材料层的厚度越薄，则电芯内阻越小，对应锂电池的电池容量降低，若要提高电池容量至预设值，则需增加负极片的数量，从而提高了锂电池的重量以及制造成本，并且造成锂电池的能量密度降低。
基于此，在本申请实施例的叠片式电芯101中，在正极片10111的长度和负极片10113的长度分别控制在135 mm～165 mm的范围内，并且正极片10111的宽度和负极片10113的宽度分别控制在135 mm～165 mm范围内的前提下，在前述极片的长度对厚度的比值范围内以及宽度对厚度的比值范围内，能够确保叠片式电芯101具有可接受的内阻，并且确保包括叠片式电芯101的锂电池具有良好的能量密度。
为了使锂电池兼顾较低的电芯内阻和较高的能量密度，在本申请的一些实施例中，正极片10111的厚度和负极片10113的厚度分别独立地选自180 μm～215 μm，例如可以是180 μm～190 μm、180 μm～200 μm、180 μm～210 μm、190 μm～200 μm、190 μm～210 μm、190 μm～215 μm、200 μm～210 μm或210 μm～215 μm，示例为180 μm、185 μm、190 μm、193 μm、197 μm、200 μm、205 μm、210 μm、215 μm或前述任意两个数值之间的值。
为了提高包含叠片式电芯101的锂电池的实际容量和循环寿命，在本申请的一些实施例中，继续参阅图2，正极活性材料层101113的材料包括磷酸锰铁锂材料，磷酸锰铁锂材料的化学通式为Li aMn xFe yM z(PO 4) b，a、x、y、z和b分别表示对应元素的摩尔量，x、y和z三者之和的数值为c，M选自Mg、Ca、Sr、Co、Ti、Zr、Mo、V、Nb、Nd、Y、Ni、Sc、Cr、Cu、Zn、Be、La以及Al中的一种或多种。
在化学通式Li aMn xFe yM z(PO 4) b中，0.10≤x≤0.70，x例如为0.10、0.20、0.30、0.40、0.50、0.60、0.70或前述任意两个数值之间的值。需要说明的是，x越高，对应磷酸锰铁锂材料中Mn的摩尔含量越高，正极片10111的平均电压越高，若x大于0.7，则在实际应用过程中可能出现锂离子扩散减弱的现象，导致正极片10111的电导率降低，从而对包含叠片式电芯101的锂电池的功率下降。
为了提高正极片10111的平均电压，并且确保正极片10111具有良好的电导率，从而提高叠片式电芯101的电化学性能，在本申请的一些实施例中，0.10≤x≤0.68、0.26≤x≤0.68、或0.4≤x≤0.68。
在化学通式Li aMn xFe yM z(PO 4) b中，a对c的比值a/c，1.01≤a/c≤1.10，a/c例如可以是1.01～1.03、1.01～1.05、1.01～1.08、1.015～1.035、1.035～1.05、1.035～1.08、1.035～1.10、1.05～1.08、或1.05～1.10，示例为1.01、1.02、1.03、1.04、1.05、1.06、1.07、1.08、1.09、1.10或前述任意两个数值之间的值。若a/c低于1.01(即Li含量较低)，则会导致磷酸锰铁锂材料的实际克容量降低，若a/c大于1.10(即Li含量较高)，则当磷酸锰铁锂材料遭受水浸润时，磷酸锰铁锂材料表面的残碱量会升高，残碱量过高则会出现锂电池“胀气”的现象，导致方形锂电池的循环性能下降。
磷的化学计量是磷酸锰铁锂材料性能的关键影响因素之一，为了确保包含磷酸锰铁锂材料的锂电池具有良好的倍率性能和循环稳定性，在化学通式Li aMn xFe yM z(PO 4) b中，a对b的比值为a/b，0.95＜a/b＜1.10，例如可以是0.95＜a/b≤1.00、0.95＜a/b≤1.03、0.95＜a/b≤1.05、0.95＜a/b≤1.08、1.00≤a/b≤1.03、1.00≤a/b≤1.08、1.00≤a/b＜1.10或1.03＜a/b＜1.10，a/b示例为0.96、0.98、1.00、1.01、1.02、1.03、1.05、1.08、1.10或前述任意两个数值之间的值；c对b的比值为c/b，0.90＜c/b＜1.10，例如可以是0.90＜c/b≤1.00、0.90＜c/b≤1.01、0.90＜c/b＜1.02、0.90＜c/b≤1.05、0.90＜c/b≤1.07、0.90＜c/b≤1.09、或0.95≤c/b≤1.10，c/b示例为0.91、0.93、0.95、0.97、0.99、1.00、1.01、1.02、1.05、1.07、1.10或前述任意两个数值之间的值。
M的元素种类是磷酸锰铁锂材料性能的关键影响因素之一，例如：M选自Mg可改善磷酸锰铁锂材料的烧结性，有利于提高包含磷酸锰铁锂材料的锂电池的倍率性能。在M为特定元素种类的前提下，M的摩尔量也会影响磷酸锰铁锂材料的性能，为了确保M对磷酸锰铁锂材料具有良好的改性效果，并且避免因M的摩尔量过高而导致电化学性能不佳，0.01≤z≤0.12，例如可以是0.01≤z≤0.03、0.01≤z≤0.05、0.01≤z≤0.08、0.01≤z≤0.10、0.05≤z≤0.08、或0.05≤z≤0.12，示例为0.01、0.02、0.03、0.05、0.08、0.10、0.12或前述任意两个数值之间的值。
为了提高磷酸锰铁锂材料的电子传输效率和离子电导率，在本申请的一些实施例中，磷酸锰铁锂材料的表面设有包覆层，包覆层的材料包括碳材料，碳材料的质量占碳材料和磷酸锰铁锂材料的质量之和的0.5%～3%。需要说明的是，包覆层对磷酸锰铁锂材料还具有保护作用，能够改善因磷酸锰铁锂材料受水分(例如电解液)浸润而导致Fe和Mn溶出，包覆层的厚度例如为3 nm～5 nm。
本申请实施例还提供了一种磷酸锰铁锂材料的制备方法，能够用于制备前文中任意一种磷酸锰铁锂材料，包括如下步骤：
S1、提供包括锂源、锰源、铁源、磷源和M源的第一浆料；
S2、对第一浆料进行研磨处理，获得第二浆料；
S3、对第二浆料进行喷雾干燥处理，获得预烧物料；
S4、对预烧物料进行烧结处理，获得磷酸锰铁锂材料。
具体的，在步骤S1中，可以根据本领域的常规方法对每一原料进行选择。锂源可以是锂的氧化物、氢氧化锂以及锂盐中的一种或多种，锂的氧化物包括但不限于是Li 2O，锂盐电离产生的阴离子包括但不限于是草酸根离子、碳酸根离子、硫酸根离子、硝酸根离子、醋酸根离子、卤素离子、磷酸根离子以及磷酸二氢根离子中的一种或多种，锂盐示例为碳酸锂、硫酸锂、硝酸锂、乙酸锂、磷酸二氢锂、磷酸锂以及草酸锂中的一种或多种。
锰源可以是锰的氧化物、氢氧化锰以及锰盐中的一种或多种，锰的氧化物包括但不限于是一氧化锰、二氧化锰以及四氧化三锰中的一种或多种，锰盐电离产生的阴离子包括但不限于是草酸根离子、碳酸根离子、硫酸根离子、硝酸根离子、醋酸根离子、卤素离子以及磷酸根离子中的一种或多种，锰源示例为碳酸锰、磷酸锰、草酸锰、硝酸锰、乙酸锰、硫酸锰以及氯化锰中的一种或多种。
铁源以是铁的氧化物、氢氧化铁以及铁盐中的一种或多种，铁的氧化物包括但不限于是四氧化三铁、三氧化二铁以及氧化亚铁中的一种或多种，铁盐电离产生的阴离子包括但不限于是草酸根离子、碳酸根离子、硫酸根离子、硝酸根离子、醋酸根离子、卤素离子以及磷酸根离子中的一种或多种，铁盐示例为硫酸亚铁、氯化铁、磷酸亚铁、磷酸铁、焦磷酸亚铁、焦磷酸铁、硝酸铁、醋酸铁、柠檬酸铁、草酸亚铁以及氯化亚铁中的一种或多种。
磷源包括但不限于是磷酸以及含磷的金属盐中的一种或多种，其中，含磷的金属盐包括但不限于是磷酸铵、磷酸二氢铵、磷酸二氢钾、磷酸二氢钠以及磷酸铁中的一种或多种。
M源例如是包含Mg、Ca、Sr、Co、Ti、Zr、Mo、V、Nb、Nd、Y、Ni、Sc、Cr、Cu、Zn、Be、La以及Al中一种或多种的化合物，化合物可以是氧化物、氢氧化物或金属盐类化合物。以M源为钛源为例，钛源可以是钛的氧化物、偏钛酸、钛酸四丁酯、氢氧化钛以及钛盐中的一种或多种，钛的氧化物包括但不限于是TiO 2，钛盐电离产生的阴离子包括但不限于是草酸根离子、碳酸根离子、硫酸根离子、硝酸根离子、醋酸根离子、卤素离子以及磷酸根离子中的一种或多种，钛盐示例为硫酸钛、硝酸钛以及氯化钛中的一种或多种；以M源为钴源为例，钴源包括但不限于四氧化三钴、硝酸钴、氧化亚钴、乙酸钴和磷酸钴中的一种或多种；以M源为镍源为例，镍源包括但不限于氧化亚镍、氧化镍、硝酸镍、乙酸镍和磷酸镍中的一种或多种；以M源为镁源为例，镁源包括但不限于氧化镁、氯化镁、硫酸镁、硝酸镁和乙酸镁中的一种或多种；以M源为锌源为例，锌源包括但不限于氧化锌、硝酸锌、硫酸锌、氯化锌和乙酸锌中的一种或多种；以M源为钒源为例，钒源包括但不限于氧化亚钒、五氧化二钒、三氧化二钒、硝酸钒和乙酸钒中的一种或多种；以D源为铌源为例，铌源包括但不限于是五氧化二妮、氢氧化铌、草酸铌、乙酸铌以及硝酸铌中的一种或多种。
需要说明的是，若制得的磷酸锰铁锂材料的表面具有包覆层，则第一浆料还包括碳源，碳源可以是无机碳源以及有机碳源中的一种或多种，其中，无机碳源包括但不限于是石墨烯、碳纳米管以及石墨中的一种或多种，有机碳源包括但不限于是葡萄糖、蔗糖、乳糖、淀粉、有机酸、维生素以及酚醛树脂中的一种或多种，碳源可以充当还原剂，有效改善烧结处理工序中Mn 2+和Fe 2+被氧化。此外，本领域技术人员知晓如何确定原料的用量以使制得的磷酸锰铁锂材料中各个元素的摩尔量达到预期值。
在步骤S1中，第一浆料的溶剂例如可以是水和/或有机溶剂，其中，水优选为去离子水，可选择的有机溶剂包括但不限于是碳原子数为1～10的醇类化合物，例如可以是甲醇、乙醇、正丙醇、2-丙醇、正丁醇、2-甲基-2-丙醇、正戊醇、2-甲基-1-丁醇以及2,2-二甲基-1-1丙醇中的一种或多种。第一浆料的溶剂优选为水，原因在于：相较于有机溶剂，水的成本较低，并且具有环保、对设备要求低、安全性高的优点。
在本申请的一些实施例中，第一浆料的固含量为10%～40%，例如可以是5%、10%、15%、20%、25%、30%、35%、40%或前述任意两个数值之间的值，使得第一浆料具有适宜的粘度以便于后续研磨处理。
在步骤S2中，研磨处理的目的在于：细化原料，能够提升后续喷雾干燥处理和烧结处理的均匀性，并且有利于在烧结处理中控制晶体生长的粒径。研磨处理的方法包括但不限于是砂磨、球磨、机械搅拌磨以及气流磨中的一种或多种。研磨处理的工艺条件可以参照本领域所采用的常规条件，例如：采用砂磨法进行研磨处理，在200 r/min～1000 r/min的转速下砂磨1 h～6 h。
在步骤S3中，喷雾干燥处理的工艺条件可以参照本领域所采用的常规条件。
在步骤S4中，烧结处理的目的在于：使所有原料发生固相反应生成磷酸锰铁锂。需要说明的是，当制得的磷酸锰铁锂材料的表面具有碳包覆层时，烧结处理需在隔绝氧气的环境下进行，例如在惰性气体氛围下进行，惰性气体包括但不限于是氮气、氩气、氦气、氩气、氖气、氪气以及氙气中的一种或多种；当制得的磷酸锰铁锂材料的表面不具有碳包覆层时，烧结处理可以在包含氧气的氛围下进行或在惰性气体氛围下进行；烧结处理所使用的设备包括但不限于是马弗炉、管式炉、回转炉、辊道窑或推板窑。
为了获得具有特定粒度的磷酸锰铁锂材料，在本申请的一些实施例中，在烧结处理的步骤之后且获得磷酸锰铁锂材料的步骤之前，磷酸锰铁锂材料的制备方法还包括步骤：对完成烧结处理获得的烧料进行粉碎处理，然后将粉碎后的物料过150目～200目的筛网以进行筛分处理，通过筛网的物料为磷酸锰铁锂材料。
对叠片式电芯101还需要说明的是，正极活性材料层101113的材料还包括正极粘结剂和正极导电剂。正极集流体101112的材料、正极粘结剂和正极导电剂可以是本领域的常规材料，例如：正极集流体101112的材料包括但不限于是铝箔或复合铝箔；正极粘结剂包括但不限于是偏氟乙烯/六氟丙烯共聚物、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯以及聚四氟乙烯中的一种或多种；正极导电剂包括但不限于是炭黑、石墨以及石墨烯中的一种或多种。
正极片10111的制备方法例如包括步骤：将磷酸锰铁锂材料、正极导电剂、正极粘结剂和第一溶剂混合以获得第一混合物；然后，将第一混合物涂覆于正极集流体101112上，然后依次进行干燥处理工序和辊压工序，获得正极片10111。可以理解的是，也可以将第一混合物在单独的载体上流延以形成膜层，然后将膜层与载体分离，再将膜层层叠设置于正极集流体101112的表面。其中，第一溶剂包括但不限于是N-甲基吡咯烷酮、二甲基甲酰胺或乙二醇二甲醚。
负极活性材料层的材料包括负极活性物质、负极粘结剂和负极导电剂。负极集流体的材料、负极活性物质、负极粘结剂和负极导电剂可以是本领域的常规材料，例如：负极集流体的材料包括但不限于是铜箔、复合铜箔或铜网；负极活性物质包括但不限于是锂单质、可与锂合金化的金属、半金属、过渡金属氧化物、非过渡金属氧化物以及碳材料中的一种或多种，可与锂合金化的金属或半金属包括但不限于是Si、Sn、Al、Ge、Pb、Bi、Sb、Si-Y 1合金(Y 1为碱金属、碱土金属、13～16族元素、过渡金属、稀土元素、或其组合，除Si之外)、以及Sn-Y 2合金(Y 2为碱金属、碱土金属、13-16族元素、过渡金属、稀土元素、或其组合，除Sn之外)，过渡金属氧化物包括但不限于是锂钛氧化物、钒氧化物、锂钒氧化物以及钛铌氧化物中的一种或多种，非过渡金属氧化物包括但不限于是SnO 2以及SiO x(0<x<2)中的一种或多种，碳材料包括但不限于是结晶碳(例如石墨)以及无定形碳中的一种或多种，负极粘结剂为去离子水或可与正极粘结剂相同，负极导电剂可与正极导电剂相同。负极片10113的制备方法可参照正极片10111的制备方法进行。
隔膜10112的材料包括但不限于是玻璃纤维、聚酯、特氟隆、聚乙烯、聚丙烯以及聚四氟乙烯中的一种或多种。
本申请实施例还提供了一种方形锂电池，如图3所示，方形锂电池10包括一个或多个如前文中任意一种叠片式电芯101，一个或多个叠片式电芯101构成方形锂电池10的电芯。
在本申请的一些实施例中，方形锂电池10的长度对宽度的比例为1.00～1.13，例如可以是1.00～1.03、1.00～1.05、1.00～1.08、1.00～1.12、1.06～1.07、或1.06～1.13，示例为1.00、1.03、1.05、1.08、1.10、1.13或前述任意两个数值之间的值。
方形锂电池的长度选自165 mm～185 mm，例如可以是165 mm～170 mm、170 mm～180 mm、174 mm～180 mm、175 mm～176 mm、或180 mm～185 mm，示例为165 mm、170 mm、175 mm、180 mm、185 mm或前述任意两个数值之间的值；和/或，方形锂电池的宽度选自155 mm～170 mm，例如可以是160 mm～170 mm、160 mm～165 mm、164 mm～165 mm、或165 mm～170 mm，示例为155 mm、160 mm、165 mm、170 mm或前述任意两个数值之间的值。
需要说明的是，当方形锂电池10作为车辆电池包的电池元件时，尤其是商用车(包括但不限于是卡车、物流车或工程车)，前述方形锂电池10的长度和宽度的尺寸设计有利于提高电池包的内部空间利用率以及续航能力，能够兼顾方形锂电池10的结构强度和散热效果。
在本申请的一些实施例中，方形锂电池10的长度对厚度的比例为3.4×10 3～4.5×10 3，例如可以是3.4×10 3～3.8×10 3、3.4×10 3～4.0×10 3、3.4×10 3～4.3×10 3、3.8×10 3～4.0×10 3、4.0×10 3～4.1×10 3、或者4.0×10 3～4.5×10 3，示例为3.4×10 3、3.8×10 3、4.0×10 3、4.5×10 3或前述任意两个数值之间的值；方形锂电池10的宽度对厚度的比例为3.3×10 2～4.3×10 2，例如可以是3.3×10 3～3.5×10 3、3.3×10 3～4.0×10 3、3.3×10 3～4.3×10 3、3.7×10 3～3.8×10 3、3.8×10 3～4.0×10 3、或者4.0×10 3～4.3×10 3，示例为3.3×10 3、3.8×10 3、4.0×10 3、4.3×10 3或前述任意两个数值之间的值。
方形锂电池10的厚度选自35 mm～55 mm，例如可以是35 mm～40 mm、35 mm～45 mm、35 mm～50 mm、40 mm～45 mm、40 mm～50 mm、43 mm～44 mm或45 mm～50 mm，示例为35 mm、40 mm、43 mm、44 mm、45 mm、50 mm、55 mm或前述任意两个数值之间的值。
需要说明的是，当方形锂电池10作为车辆电池包的电池元件时，尤其是商用车(包括但不限于是卡车、物流车或工程车)，前述方形锂电池10的长度对厚度的比例设计以及宽度对厚度的比例设计能够优化电池包中方形锂电池10的能量在空间上的分布；此外，前述方形锂电池10的厚度尺寸设计能够确保电池包中任意相邻两个方形锂电池10之间具有足够的散热面积，从而保证散热效果，并且降低了单个方形锂电池10的体积占比，有利于多个方形锂电池10在电池包内的紧凑化布置。
需要说明的是，方形锂电池10还包括其他常规结构件，例如继续参阅图1和图3，方形锂电池10还包括壳体102、正极柱103和负极柱104，正极柱103和负极柱104分别设置于壳体102的表面，叠片式电芯101设置于壳体102内，壳体102的材料例如为铝。其中，通过点焊工艺将正极耳1012与正极柱103通过连接片105焊接于一体以形成方形锂电池10的正极，以及通过点焊工艺将负极耳1013与负极柱104通过连接片105焊接于一体以形成方形锂电池10的负极。
此外，方形锂电池10还包括电解液，电解液浸润叠片式电芯101。电解液可以是本领域常规的成分组成，例如：电解液包括锂盐和有机溶剂，其中，有机溶剂例如选自碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、亚硫酸丙烯酯、乙酸乙酯、亚硫酸二乙酯、1,3-丙烷磺酸内酯中的两种或两种以上的组合；锂盐例如选自LiPF 6、LiClO 4、LiBF 4、LiSbF 6、LiAsF 6、LiCF 3SO 3、Li(CF 3SO 2) 2N、LiC 4F 9SO 3、LiAlO 2、LiAlCl 4、LiODFB 、LiTFSI、LiFSI、LiCl、LiI以及LiN(C xF 2x+1SO 2)(C yF 2y+1SO 2)中的一种或多种，其中，x和y分别为1～20的整数，锂盐的质量占电解液的总质量的比例示例为10%～15%。
在本申请的一些实施例中，方形锂电池10的电芯(由一个或多个叠片式电芯101组成)在25 ℃下的交流内阻为0.2 mΩ～0.5 mΩ，和/或方形锂电池的能量密度为190 Wh/kg～220 Wh/kg，和/或方形锂电池的容量为175 Ah～250 Ah，和/或方形锂电池的电压为2.5 V～4.2 V。
本申请实施例还提供了一种电池包，如图4所示，电池包100包括箱体20和多个如前文中任意一种方形锂电池10，箱体20形成有容纳空间201，多个方形锂电池10依序排列于容纳空间201内。
需要说明的是，电池包100还包括其他常规结构件，例如继续参阅图4，电池包100还包括盖体30和缓冲件40，盖体30用于遮盖箱体20的内部空间，缓冲件40设置于箱体20内且位于箱体20的箱壁202。可以理解的是，电池包100还可以包括电池管理系统、冷却装置等部件。
本申请实施例还提供了一种如前文中任意一种叠片式电芯、或如前文中任意一种方形锂电池、或如前文中任意一种电池包在车辆中的应用，其中，电芯、或方形锂电池、或电池包作为车辆的动力来源。
在本申请的一些实施例中，车辆选自卡车、物流车或工程车。
下面通过具体实施例、对比例和实验例对本申请的技术方案及技术效果进行详细说明，以下实施例是本申请的部分实施例，并非对本申请作出具体限定。
实施例1
本实施例提供了一种方形锂电池，如图3所示，方形锂电池10包括叠片式电芯101、壳体102、正极柱103和负极柱104，其中，叠片式电芯101设置于壳体102内，壳体102的材料例如为铝，正极柱103和负极柱104分别设置于壳体102的表面。其中，如图1所示，叠片式电芯101包括沿着第一方向X1依次层叠设置的55个电芯单元1011，每一电芯单元1011包括依次层叠设置的一正极片10111、一隔膜10112以及一负极片10113，第一方向X1垂直于正极片10111靠近隔膜10112的第一面101111，所有电芯单元1011的正极片10111的子极耳101110依次连接而形成正极耳1012，且所有电芯单元1011的负极片10113的子极耳101110依次连接而形成负极耳1013。继续参阅图3，正极耳1012和负极耳1013分别位于壳体102的开口处，正极耳1012与正极柱103焊接于一体以形成方形锂电池10的正极，负极耳1013与负极柱104焊接于一体以形成方形锂电池10的负极。方形锂电池10还包括电解液，电解液浸润叠片式电芯101。
如图2所示，正极片10111包括正极集流体101112和正极活性材料层101113，正极活性材料层101113设置于正极集流体101112的表面，正极集流体101112的材料为涂碳铝箔(厚度为12 μm)，正极活性材料层101113的材料包括碳材料包覆的Li 0.96Fe 0.3Mn 0.6Mg 0.04PO 4，包覆层的平均厚度为3 nm，碳材料的质量占碳材料和Li 0.96Fe 0.3Mn 0.6Mg 0.04PO 4的总质量的1.5%。
正极片10111的制备方法包括如下步骤：按照碳材料包覆的Li 0.96Fe 0.3Mn 0.6Mg 0.04PO 4：炭黑导电(Super PLL)：碳纳米管：聚偏二氟乙烯的质量比为97:0.4:0.5:2.1的质量比称取前述四者原料，将前述四者原料与N-甲基吡咯烷酮混合均匀以获得正极浆料，正极浆料的固含量为65%；然后，通过涂覆机将正极浆料涂覆于厚度为12 μm的铝箔上(双面均涂覆)，然后置于120 ℃下烘烤固化以形成正极活性材料层，再通过辊压机冷压至相应的厚度，获得正极片。
其中，碳材料包覆的Li 0.96Fe 0.3Mn 0.6V 0.04PO 4的制备方法包括如下步骤：
S1.1、取45.76 kg的四氧化三锰、45.25 kg的磷酸铁、35.46 kg的碳酸锂、1.6 kg的氧化镁、80.68 kg的质量百分数为85%的磷酸水溶液以及2.72 kg的葡萄糖加入混料机以混合原料，混合时间为2 h，获得混合物料，然后将混合物料转移至砂磨机，按照混合料的质量对去离子水的质量比为1：1.5向混合物料中加入去离子水，获得第一浆料；
S1.2、对第一浆料进行砂磨处理，砂磨处理的工艺参数为：砂磨转速为500 r/min，砂磨时间为1.5 h，获得第二浆料；
S1.3、将第二浆料进行一次喷雾干燥处理，在整个喷雾干燥处理的过程中保证浆料处于搅拌状态，获得预烧物料，预烧物料的粒径分布范围为2 μm～5 μm；
S1.4、将预烧物料置于窑炉中，通入保护气体N 2，N 2的流量为 80 mL/min，然后以5 ℃/min的升温速率从室温升温至750 ℃，并于750 ℃下烧结6 h，冷却至室温，获得烧料；
S1.5、将烧料依次进行气流粉碎处理和150目筛网筛分处理，将通过150目筛网的物料进行去除铁单质处理工序，获得碳材料包覆的Li 0.96Fe 0.3Mn 0.6V 0.04PO 4。
负极片10113包括负极集流体和负极活性材料层，负极活性材料层设置于负极集流体的表面，负极集流体的材料为铝箔(厚度为12 μm)，负极活性材料层的材料包括石墨。负极片10113的制备方法包括步骤：按照石墨:导电炭黑(Super PLL):羧甲基纤维素:丁苯橡胶质量比为97:0.7:1.25:1.05的质量比称取前述四者原料，将前述四者原料与N-甲基吡咯烷酮混合均匀以获得负极浆料，负极浆料的固含量为55%；然后，通过涂覆机将负极浆料涂覆于厚度为8 μm的铝箔上(双面均涂覆)，然后置于80 ℃下烘烤固化以形成负极活性材料层，再通过辊压机冷压至相应的厚度，获得负极片。
电解液的制备方法包括步骤：按照碳酸乙烯酯(EC)：碳酸二乙酯(DEC)：碳酸甲乙酯(EMC) 4：3：3的体积比将前述三者混合以获得溶剂，然后向溶剂中加入LiPF 6和添加剂，混合均匀获得电解液，电解液中LiPF 6的浓度为1.0 mol/L，添加剂的质量占电解液的总质量的10%，添加剂由碳酸亚乙烯酯、1,3-丙烷磺酸内酯、氟代碳酸乙烯酯和环己基苯组成，碳酸亚乙烯酯：1,3-丙烷磺酸内酯：氟代碳酸亚乙烯酯：环己基苯的质量比为3：2：1：1。
方形锂电池10的制备方法包括步骤：将一正极片10111、一厚度为12 μm的PP隔膜10112以及一负极片10113通过叠片方式形成一电芯单元1011，将55个电芯单元1011通过叠片方式形成一叠片式电芯101，将2个叠片式电芯101与铝壳进行组装，然后注入电解液，再经过老化、化成、整形、封装等工序制得方形锂电池10。
本实施例中正极片10111和负极片10113的尺寸完全相同(正极活性材料层和负极活性材料层的尺寸完全相同)。本实施例中正极片10111、负极片10113以及方形锂电池10的尺寸如下表1所示：
表1
项目 数值
正极片(负极片)的长度(mm) 151
正极片(负极片)的宽度(mm) 148
正极片(负极片)的厚度(μm) 197
方形锂电池的长度(mm) 175
方形锂电池的宽度(mm) 164
方形锂电池的厚度(mm) 43
实施例2
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的厚度分别替换为“190 μm”。
实施例3
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的厚度分别替换为“180 μm”。
实施例4
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的厚度分别替换为“210 μm”。
实施例5
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的厚度分别替换为“215 μm”。
实施例6
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的宽度分别替换为“145 mm”。
实施例7
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的宽度分别替换为“155 mm”。
实施例8
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的宽度分别替换为“135 mm”。
实施例9
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的宽度分别替换为“165 mm”。
实施例10
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的长度分别替换为“145 mm”。
实施例11
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的长度分别替换为“155 mm”。
实施例12
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的长度分别替换为“135 mm”。
实施例13
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的长度分别替换为“165 mm”。
实施例14
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的长度分别替换为“145 mm”，以及将正极片和负极片的宽度分别替换为“140 mm”。
实施例15
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的长度分别替换为“150 mm”，以及将正极片和负极片的宽度分别替换为“140 mm”。
实施例16
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的长度分别替换为“155 mm”，以及将正极片和负极片的宽度分别替换为“155 mm”。
实施例17
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极片和负极片的长度分别替换为“165 mm”，以及将正极片和负极片的宽度分别替换为“135 mm”。
实施例18
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将方形锂电池的厚度替换为“35 mm”。
实施例19
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将方形锂电池的厚度替换为“55 mm”。
实施例20
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将方形锂电池的厚度替换为“40 mm”。
实施例21
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将方形锂电池的厚度替换为“50 mm”。
实施例22
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将方形锂电池的宽度替换为“170 mm”。
实施例23
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将方形锂电池的宽度替换为“155 mm”。
实施例24
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将方形锂电池的长度替换为“165 mm”。
实施例25
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将方形锂电池的长度替换为“185 mm”。
实施例26
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极活性材料层101113中的“Li 0.96Fe 0.3Mn 0.6Mg 0.04PO 4”替换为“Li 0.96Fe 0.3Mn 0.6V 0.04PO 4”。
其中，Li 0.96Fe 0.3Mn 0.6V 0.04PO 4的制备方法包括步骤：将步骤S1.1中“1.6 kg的氧化镁”替换为“3 kg的三氧化二钒”。
实施例27
本实施例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本实施例中方形锂电池的区别之处仅在于：将正极活性材料层101113中的“Li 0.96Fe 0.3Mn 0.6Mg 0.04PO 4”替换为“Li 0.96Fe 0.3Mn 0.6Mg 0.02V 0.02PO 4”。
其中，Li 0.96Fe 0.3Mn 0.6Mg 0.02V 0.02PO 4的制备方法包括步骤：将步骤S1.1中“1.6 kg的氧化镁”替换为“0.8 kg的氧化镁和1.5 kg的三氧化二钒”。
对比例1
本对比例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本对比例中方形锂电池的区别之处仅在于：将正极片和负极片的厚度分别替换为“250 μm”。
对比例2
本对比例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本对比例中方形锂电池的区别之处仅在于：将正极片和负极片的宽度分别替换为“110 mm”。
对比例3
本对比例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本对比例中方形锂电池的区别之处仅在于：将正极片和负极片的长度分别替换为“110 mm”。
对比例4
本对比例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本对比例中方形锂电池的区别之处仅在于：将方形锂电池的宽度替换为“140 mm”。
对比例5
本对比例提供了一种方形锂电池，相较于实施例1中提供的方形锂电池，本对比例中方形锂电池的区别之处仅在于：将方形锂电池的长度替换为“150 mm。
实验例1
分别对实施例1至实施例17、实施例26以及对比例1至对比例3中方形锂电池的电芯交流内阻进行检测(25 ℃)，检测结果如下表2所示：
表2
编号 电芯交流内阻(mΩ)
实施例1 0.31
实施例2 0.29
实施例3 0.26
实施例4 0.33
实施例5 0.34
实施例6 0.31
实施例7 0.32
实施例8 0.28
实施例9 0.37
实施例10 0.30
实施例11 0.31
实施例12 0.27
实施例13 0.33
实施例14 0.29
实施例15 0.31
实施例16 0.33
实施例17 0.32
实施例26 0.31
实施例27 0.28
对比例1 0.62
对比例2 0.38
对比例3 0.37
由表2可知，相较于对比例1至对比例3中方形锂电池的电芯交流内阻(25 ℃)，实施例1至实施例26中方形锂电池的电芯交流内阻(25 ℃)较小。
实验例2
分别对实施例1至实施例26以及对比例1至对比例5中的方形锂电池进行电性能测试和热失控测试，其中，电性能测试方法包括步骤：将每一方形锂电池在25 ℃下以0.2C倍率恒流恒压-充电至4.2 V，其中恒压充电截止电流为0.02C，随后以0.2C恒流-放电直至电压达到2.5V，获得在25 ℃、0.2C倍率条件下的首次放电容量和首次充电容量，并计算获得各个方形锂电池在25 ℃、0.2C倍率条件下的首次充放电效率(首次放电容量对首次充电容量的比值×100%)。热失控测试的检测方法参照GB38032-2020 附录A热失控测试方法进行。
检测结果如下表3所示：
表3
编号 首次充电容量(mAh/g) 首次放电容量(mAh/g) 首次充放电 效率 (%) 热失控测试
实施例1 139.32 158.5 87.9 通过
实施例2 139.44 157.2 88.7 通过
实施例3 139.35 155.7 89.5 通过
实施例4 138.71 159.8 86.8 通过
实施例5 136.74 160.3 85.3 通过
实施例6 135.12 160.1 84.4 通过
实施例7 136.00 162.1 83.9 通过
实施例8 131.30 162.9 80.6 通过
实施例9 137.23 158.1 86.8 通过
实施例10 139.11 157.9 88.1 通过
实施例11 138.82 159.2 87.2 通过
实施例12 132.80 153.7 86.4 通过
实施例13 128.56 160.5 80.1 通过
实施例14 137.43 157.6 87.2 通过
实施例15 138.02 157.2 87.8 通过
实施例16 140.34 158.4 88.6 通过
实施例17 137.56 159.4 86.3 通过
实施例18 137.57 157.4 87.4 通过
实施例19 140.84 161.7 87.1 通过
实施例20 137.85 157.9 87.3 通过
实施例21 138.46 158.6 87.3 通过
实施例22 133.74 156.6 85.4 通过
实施例23 131.00 154.3 84.9 通过
实施例24 137.51 158.6 86.7 通过
实施例25 135.18 155.2 87.1 通过
实施例26 139.37 158.2 88.1 通过
实施例27 143.69 159.3 90.2 通过
对比例1 124.88 164.1 76.1 通过
对比例2 120.58 154.2 78.2 通过
对比例3 115.14 152.3 75.6 通过
对比例4 114.63 156.6 73.2 不通过
对比例5 115.77 157.3 73.6 不通过
由表2和表3可知，相较于对比例1至对比例5中方形锂电池，实施例1至实施例26中方形锂电池的综合性能更佳。由此可知，在方形锂电池中，在正极片的长度和负极片的长度分别控制在135 mm～165 mm的范围内，以及正极片的宽度和负极片的宽度分别控制在135 mm～165 mm范围内，以及正极片的厚度和负极片的厚度分别控制在190 μm～210 mm范围内，以及方形锂电池的长度控制在165 mm～185 mm范围内，以及方形锂电池的宽度控制在155 mm～170 mm范围内，以及方形锂电池的厚度控制在35 mm～55 mm范围内，能够确保方形锂电池的电芯具有可接受的内阻，并且能够提升方形锂电池的实际容量、能量密度、倍率性能和循环稳定性，并且方形锂电池具有良好的安全性。

Claims (16)

  1. 一种叠片式电芯，其中，所述叠片式电芯包括沿着第一方向依次层叠设置的多个电芯单元，每一所述电芯单元包括依次层叠设置的一正极片、一隔膜以及一负极片，并且相邻两个所述电芯单元之间设有一所述隔膜，所述第一方向垂直于所述正极片靠近所述隔膜的第一面，每一所述电芯单元的所述正极片设有子极耳，每一所述电芯单元的所述负极片设有子极耳；多个所述电芯单元的正极片的子极耳依次连接而形成正极耳，多个所述电芯单元的负极片的子极耳依次连接而形成负极耳；
    所述正极片的长度对厚度的比值以及所述负极片的长度对厚度的比值分别独立地选自6.3×10 2 ～9.4×10 2 ，所述正极片的宽度对厚度的比值以及所述负极片的宽度对厚度的比值分别独立地选自6.3×10 2 ～9.4×10 2 。
  2. 根据权利要求1所述的叠片式电芯，其中，所述正极片的长度和所述负极片的长度分别独立地选自135 mm～165 mm，所述正极片的宽度和所述负极片的宽度分别独立地选自135 mm～165 mm；和/或
    所述正极片的厚度和所述负极片的厚度分别独立地选自180 μm～215 μm；和/或
    所述正极片的尺寸与所述负极片的尺寸相同。
  3. 根据权利要求1或2所述的叠片式电芯，其中，所述正极片的长度和所述负极片的长度分别为145 mm～155 mm；和/或
    所述正极片的宽度和所述负极片的宽度分别为145 mm～155 mm；和/或
    所述正极片的长度对厚度的比值以及所述负极片的长度对厚度的比值分别为7.7×10 2 ～8.5×10 2 ；和/或
    所述正极片的宽度对厚度的比值以及所述负极片的宽度对厚度的比值分别为7.7×10 2 ～8.5×10 2 ；和/或
    所述正极片的厚度和所述负极片的厚度分别独立地选自190 μm～210 μm。
  4. 根据权利要求1至3任一项中所述的叠片式电芯，其中，所述正极片包括正极集流体以及设置于所述正极集流体的表面的正极活性材料层；所述正极活性材料层的材料包括磷酸锰铁锂材料，所述磷酸锰铁锂材料的化学通式为Li a Mn x Fe y M z (PO 4 ) b ，a、x、y、z和b分别表示对应元素的摩尔量，x、y和z三者之和的数值为c，M选自Mg、Ca、Sr、Co、Ti、Zr、Mo、V、Nb、Nd、Y、Ni、Sc、Cr、Cu、Zn、Be、La以及Al中的一种或多种；
    其中，0.10≤x≤0.70，0.01≤z≤0.12；a对c的比值为a/c，1.01≤a/c≤1.10；a对b的比值为a/b，0.95＜a/b＜1.10；c对b的比值为c/b，0.90＜c/b＜1.10。
  5. 根据权利要求4所述的叠片式电芯，其中，在所述磷酸锰铁锂材料中，0.26≤x≤0.68，和/或0.01≤z≤0.05，和/或1.015≤a/c≤1.035，和/或0.95＜a/b＜1.03，和/或0.90＜c/b＜1.02；和/或
    所述磷酸锰铁锂材料的表面设有包覆层，所述包覆层的材料包括碳材料，所述碳材料的质量占所述碳材料和所述磷酸锰铁锂材料的质量之和的0.5%～3%。
  6. 一种方形锂电池，其中，所述方形锂电池包括一个或多个叠片式电芯，每一所述叠片式电芯包括沿着第一方向依次层叠设置的多个电芯单元，每一所述电芯单元包括依次层叠设置的一正极片、一隔膜以及一负极片，并且相邻两个所述电芯单元之间设有一所述隔膜，所述第一方向垂直于所述正极片靠近所述隔膜的第一面，每一所述电芯单元的所述正极片设有子极耳，每一所述电芯单元的所述负极片设有子极耳；多个所述电芯单元的正极片的子极耳依次连接而形成正极耳，多个所述电芯单元的负极片的子极耳依次连接而形成负极耳；
    所述正极片的长度对厚度的比值以及所述负极片的长度对厚度的比值分别独立地选自6.3×10 2 ～9.4×10 2 ，所述正极片的宽度对厚度的比值以及所述负极片的宽度对厚度的比值分别独立地选自6.3×10 2 ～9.4×10 2 。
  7. 根据权利要求6所述的方形锂电池，其中，所述正极片的长度和所述负极片的长度分别独立地选自135 mm～165 mm，所述正极片的宽度和所述负极片的宽度分别独立地选自135 mm～165 mm；和/或
    所述正极片的厚度和所述负极片的厚度分别独立地选自180 μm～215 μm；和/或
    所述正极片的尺寸与所述负极片的尺寸相同；和/或
    所述正极片包括正极集流体以及设置于所述正极集流体的表面的正极活性材料层；所述正极活性材料层的材料包括磷酸锰铁锂材料，所述磷酸锰铁锂材料的化学通式为Li a Mn x Fe y M z (PO 4 ) b ，a、x、y、z和b分别表示对应元素的摩尔量，x、y和z三者之和的数值为c，M选自Mg、Ca、Sr、Co、Ti、Zr、Mo、V、Nb、Nd、Y、Ni、Sc、Cr、Cu、Zn、Be、La以及Al中的一种或多种，0.10≤x≤0.70，0.01≤z≤0.12；a对c的比值为a/c，1.01≤a/c≤1.10；a对b的比值为a/b，0.95＜a/b＜1.10；c对b的比值为c/b，0.90＜c/b＜1.10。
  8. 根据权利要求6或7所述的方形锂电池，其中，所述方形锂电池的长度对宽度的比例为1.00～1.13，所述方形锂电池的长度对厚度的比例为3.4×10 3 ～4.5×10 3 ，所述方形锂电池的宽度对厚度的比例为3.3×10 2 ～4.3×10 2 ；和/或
    所述方形锂电池还包括壳体，所述叠片式电芯设置于所述壳体内；和/或
    所述方形锂电池的电芯在25 ℃下的交流内阻为0.2 mΩ～0.5 mΩ，和/或所述方形锂电池的能量密度为190 Wh/kg～220 Wh/kg，和/或所述方形锂电池的容量为175 Ah～250 Ah，和/或所述方形锂电池的电压为2.5 V～4.2 V。
  9. 根据权利要求6至8任一项中所述的方形锂电池，其中，所述方形锂电池的长度对宽度的比例为1.06～1.07；和/或
    所述方形锂电池的长度对厚度的比例为4.0×10 3 ～4.1×10 3 ；和/或
    所述方形锂电池的宽度对厚度的比例为3.7×10 2 ～3.8×10 2 ；和/或
    所述方形锂电池的长度选自165 mm～185 mm；和/或
    所述方形锂电池的宽度选自155 mm～170 mm；和/或
    所述方形锂电池的厚度选自35 mm～55 mm。
  10. 根据权利要求6至9任一项中所述的方形锂电池，其中，所述方形锂电池的长度选自170 mm～180 mm；和/或
    所述方形锂电池的宽度选自160 mm～170 mm；和/或
    所述方形锂电池的厚度选自40 mm～50 mm。
  11. 根据权利要求6至10任一项中所述的方形锂电池，其中，所述方形锂电池的长度选自174 mm～180 mm；和/或
    所述方形锂电池的宽度选自160 mm～165 mm；和/或
    所述方形锂电池的厚度选自40 mm～45 mm。
  12. 一种电池包，其中，所述电池包包括箱体以及多个方形锂电池，所述箱体形成有容纳空间，多个所述方形锂电池依序排列于所述容纳空间内；
    所述方形锂电池包括一个或多个叠片式电芯，每一所述叠片式电芯包括沿着第一方向依次层叠设置的多个电芯单元，每一所述电芯单元包括依次层叠设置的一正极片、一隔膜以及一负极片，并且相邻两个所述电芯单元之间设有一所述隔膜，所述第一方向垂直于所述正极片靠近所述隔膜的第一面，每一所述电芯单元的所述正极片设有子极耳，每一所述电芯单元的所述负极片设有子极耳；多个所述电芯单元的正极片的子极耳依次连接而形成正极耳，多个所述电芯单元的负极片的子极耳依次连接而形成负极耳；
    所述正极片的长度对厚度的比值以及所述负极片的长度对厚度的比值分别独立地选自6.3×10 2 ～9.4×10 2 ，所述正极片的宽度对厚度的比值以及所述负极片的宽度对厚度的比值分别独立地选自6.3×10 2 ～9.4×10 2 。
  13. 根据权利要求12所述的电池包，其中，所述正极片的长度和所述负极片的长度分别独立地选自135 mm～165 mm，所述正极片的宽度和所述负极片的宽度分别独立地选自135 mm～165 mm；和/或
    所述正极片的厚度和所述负极片的厚度分别独立地选自180 μm～215 μm；和/或
    所述正极片的尺寸与所述负极片的尺寸相同；和/或
    所述正极片包括正极集流体以及设置于所述正极集流体的表面的正极活性材料层；所述正极活性材料层的材料包括磷酸锰铁锂材料，所述磷酸锰铁锂材料的化学通式为Li a Mn x Fe y M z (PO 4 ) b ，a、x、y、z和b分别表示对应元素的摩尔量，x、y和z三者之和的数值为c，M选自Mg、Ca、Sr、Co、Ti、Zr、Mo、V、Nb、Nd、Y、Ni、Sc、Cr、Cu、Zn、Be、La以及Al中的一种或多种，0.10≤x≤0.70，0.01≤z≤0.12；a对c的比值为a/c，1.01≤a/c≤1.10；a对b的比值为a/b，0.95＜a/b＜1.10；c对b的比值为c/b，0.90＜c/b＜1.10。
  14. 根据权利要求12或13所述的电池包，其中，所述方形锂电池的长度对宽度的比例为1.00～1.13，所述方形锂电池的长度对厚度的比例为3.4×10 3 ～4.5×10 3 ，所述方形锂电池的宽度对厚度的比例为3.3×10 2 ～4.3×10 2 ；和/或
    所述方形锂电池还包括壳体，所述叠片式电芯设置于所述壳体内；和/或
    所述方形锂电池的电芯在25 ℃下的交流内阻为0.2 mΩ～0.5 mΩ，和/或所述方形锂电池的能量密度为190 Wh/kg～220 Wh/kg，和/或所述方形锂电池的容量为175 Ah～250 Ah，和/或所述方形锂电池的电压为2.5 V～4.2 V；和/或
    所述方形锂电池的长度选自165 mm～185 mm；和/或
    所述方形锂电池的宽度选自155 mm～170 mm；和/或
    所述方形锂电池的厚度选自35 mm～55 mm。
  15. 根据权利要求12至14任一项中所述的电池包，其中，所述电池包作为车辆的动力来源。
  16. 根据权利要求15所述的电池包，其中，所述车辆选自卡车、物流车或工程车。
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