WO2021109080A1 - 锂离子电池、用于锂离子电池的正极极片及装置 - Google Patents

锂离子电池、用于锂离子电池的正极极片及装置 Download PDF

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WO2021109080A1
WO2021109080A1 PCT/CN2019/123338 CN2019123338W WO2021109080A1 WO 2021109080 A1 WO2021109080 A1 WO 2021109080A1 CN 2019123338 W CN2019123338 W CN 2019123338W WO 2021109080 A1 WO2021109080 A1 WO 2021109080A1
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positive electrode
active material
electrode active
lithium ion
ion battery
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PCT/CN2019/123338
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English (en)
French (fr)
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李全国
刘立乐
胡霞
牛少军
伍永彬
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宁德时代新能源科技股份有限公司
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Priority to CN201980098900.5A priority Critical patent/CN114245940B/zh
Priority to PCT/CN2019/123338 priority patent/WO2021109080A1/zh
Priority to EP19932224.9A priority patent/EP3859824A4/en
Priority to US17/135,540 priority patent/US20210175511A1/en
Publication of WO2021109080A1 publication Critical patent/WO2021109080A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
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    • 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
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
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    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • H—ELECTRICITY
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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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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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    • 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
    • H—ELECTRICITY
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    • 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
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    • 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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
    • H01M2010/4271—Battery management systems including electronic circuits, e.g. control of current or voltage to keep battery in healthy state, cell balancing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2200/00—Safety devices for primary or secondary batteries
    • H01M2200/10—Temperature sensitive devices
    • H01M2200/106—PTC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

Definitions

  • This application relates to the field of batteries, and in particular, to a lithium ion battery, a positive electrode piece and a device for the lithium ion battery.
  • the mass-produced batteries on the market are mainly lithium iron phosphate system and ternary system batteries. Both of these batteries have one thing in common that the battery has a higher discharge power under high SOC (state of charge), and its power It can support the instantaneous acceleration of the car, but the instantaneous output power of the battery in the low SOC state cannot meet the instantaneous acceleration of the car in the low battery.
  • the general improvement methods at this stage are: 1) Reduce the coating weight of the active material on the current collector of the battery to increase the maximum charge and discharge current of the battery.
  • the disadvantages of this method It reduces the proportion of active materials in the weight of the entire battery cell, thereby reducing the mass energy density of the battery cell: 2) Select active materials with better dynamic performance, and increase the content of conductive carbon to increase the maximum charge and discharge current.
  • the disadvantage of this method is that it increases the raw material cost of the battery: 3) Choose an electrolyte with high ionic conductivity to increase the ion conductivity to increase the maximum charge and discharge current.
  • the disadvantage of this method is that the cost is increased, and at the same time, electrolysis is performed during the cycle of battery charging and discharging. The liquid is easily decomposed, causing excessive pressure inside the battery, which may easily cause safety accidents.
  • the purpose of this application is to provide a lithium ion battery to solve the current problem of low instantaneous output power of lithium ion batteries in a low SOC state; and to provide a positive pole piece and device for lithium ion batteries.
  • a lithium ion battery which includes a positive pole piece, the positive pole piece includes a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector, the positive electrode active material
  • the positive active material in the layer includes a positive active material I and a positive active material II, the positive active material I is a layered lithium nickel transition metal oxide, and the positive active material II is an olivine-type lithium-containing phosphate,
  • the positive pole piece satisfies: 2.5 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 21,
  • A is the mass percentage of the positive electrode active material II in the total weight of the positive electrode active material
  • N is the number of the positive electrode active material I particles contained in the positive electrode active material layer along the thickness direction of the positive electrode active material layer;
  • PD is the compacted density of the positive pole piece, in g/cm 3 ;
  • P 1 is the porosity of the positive pole piece.
  • the present application provides a positive electrode piece for a lithium ion battery, the positive electrode piece comprising a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector, the positive electrode active material
  • the positive active material in the layer includes a positive active material I and a positive active material II, the positive active material I is a layered lithium nickel transition metal oxide, and the positive active material II is an olivine-type lithium-containing phosphate,
  • the positive pole piece satisfies: 2.5 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 21,
  • A is the mass percentage of the positive electrode active material II in the total weight of the positive electrode active material
  • N is the number of the positive electrode active material I particles contained in the positive electrode active material layer along the thickness direction of the positive electrode active material layer;
  • PD is the compacted density of the positive pole piece, in g/cm 3 ;
  • P 1 is the porosity of the positive pole piece.
  • the third aspect of the present application provides a device including the lithium ion battery described in the first aspect of the present application, and the lithium ion battery is used as a power source for the device.
  • the positive electrode sheet includes a positive electrode active material layer, wherein the positive electrode active material layer includes a positive electrode active material I and a positive electrode active material II, and the positive electrode active material I is a layered lithium nickel transition metal oxide.
  • Substance II is olivine-type lithium-containing phosphate.
  • the above-mentioned positive pole piece satisfies 2.5 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 21. When the positive pole piece satisfies this relationship, lithium The ion battery can obtain a larger discharge current and discharge power at a low SOC, and can especially meet the instantaneous acceleration requirements of existing power vehicles for lithium-ion batteries in a low SOC state.
  • the lithium ion battery provided in the present application is based on the rational setting of the active material particle size distribution, relative percentage content, and active material on the positive electrode plate layer of the layered lithium nickel transition metal oxide and the olivine-type lithium-containing phosphate in the positive electrode active material.
  • the device of the present application includes the lithium ion battery described in the present application, and therefore has at least the same advantages as the lithium ion battery.
  • FIG. 1 is a perspective view of an embodiment of a lithium ion battery
  • Figure 2 is an exploded view of an embodiment of a lithium ion battery
  • Fig. 3 is a perspective view of an embodiment of a battery module
  • Figure 4 is a perspective view of an embodiment of the battery pack
  • Figure 5 is an exploded view of Figure 4.
  • Fig. 6 is a schematic diagram of an embodiment of a device using a lithium ion battery as a power source.
  • the present application provides a lithium ion battery, including a positive pole piece, the positive pole piece including a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector, so
  • the positive electrode active material in the positive electrode active material layer includes a positive electrode active material I and a positive electrode active material II, the positive electrode active material I is a layered lithium nickel transition metal oxide, and the positive electrode active material II is an olivine-type lithium-containing phosphoric acid salt,
  • the positive pole piece satisfies: 2.5 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 21,
  • A is the mass percentage of the positive electrode active material II in the total weight of the positive electrode active material
  • N is the number of the positive electrode active material I particles contained in the positive electrode active material layer along the thickness direction of the positive electrode active material layer;
  • PD is the compacted density of the positive pole piece, in g/cm 3 ;
  • P 1 is the porosity of the positive pole piece.
  • the lithium ion battery provided in the present application is based on the rational setting of the active material particle size distribution, relative percentage content, and active material on the positive electrode plate layer of the layered lithium nickel transition metal oxide and the olivine-type lithium-containing phosphate in the positive electrode active material.
  • the spacing between the particles, as well as the compaction density and porosity of the entire positive pole piece optimizes the lithium ion transmission rate and charge and discharge power in the positive pole piece, thereby achieving the purpose of increasing the instantaneous discharge power of the battery under low SOC.
  • the output characteristics of the power at the low SOC of the positive pole piece level and the spacing between the active material particles, the compaction density and porosity of the positive pole piece are compared with the positive electrode active material I and the positive electrode active material II.
  • the type, respective particle shape, particle size distribution, and the overall particle size distribution of the two are closely related.
  • the positive electrode active material I in the present application has a single particle morphology, 6 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 21, preferably 8 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 19.
  • the positive electrode active material I in the present application has a secondary particle morphology, 2.5 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 9, preferably It is 3 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 8.
  • the number N of the positive electrode active material I particles contained in the positive electrode active material layer is 6 to 55, preferably 7 to 40. More preferably, when the positive electrode active material I is a single particle, N is 20 to 40; when the positive electrode active material I is a secondary particle, N is 6 to 20.
  • the porosity of the overall positive electrode piece can be adjusted, and the transmission of lithium ions in the positive electrode active material I can be ensured, so that the positive electrode piece maintains a better charge. Discharge power.
  • the value range of N includes but is not limited to, for example, 7, 10, 12, 15, 17, 20, 23, 25, 28, 30, 32.
  • N is the number of the positive electrode active material I particles contained in the positive electrode active material layer along the thickness direction of the positive electrode active material layer.
  • N for any 10 positions of the positive pole piece, cross-sections are made along the thickness direction of the positive pole piece, and the number of particles of the positive electrode active material I arranged in the thickness direction is calculated as N 1 , N 2 , N 3 , ⁇ N 9 , N 10 , and calculate the average value as N, that is, in the thickness direction, the average number of particles of the positive electrode active material I contained in the positive electrode active material layer, thus Calculate the value of N.
  • magnification 1000 to 5000 times.
  • the positive electrode active material I has a single particle morphology, because the material particles are small, it is preferred to use 5000 times magnification for measurement; when the positive electrode active material I has a secondary particle morphology, because the material particles are larger, it is preferable to use 1000 times Zoom in and measure.
  • the mass percentage A of the positive electrode active material II to the total weight of the positive electrode active material satisfies: 2% ⁇ A ⁇ 40%, preferably 10% ⁇ A ⁇ 20%.
  • the proportion A of the positive electrode active material II is within the above range, the corresponding lithium ion battery has better low SOC charge and discharge power performance, and the volume energy density of the single battery is higher.
  • the porosity P 1 of the positive pole piece satisfies: 19% ⁇ P 1 ⁇ 25%, and a preferred range is 20% ⁇ P 1 ⁇ 25%.
  • the porosity of the positive pole piece can be tested with a porosity tester.
  • the porosity of the positive pole piece is controlled within the above range, on the one hand, it can ensure that the relative content of the active material that can be loaded in the positive pole piece is relatively large, which is beneficial to increase the volume energy density of the battery, and at the same time, it can ensure that the lithium ion can be fast Into the inside of the pole piece makes the charge and discharge power of the lithium ion battery using the positive pole piece better.
  • the compacted density PD of the positive pole piece satisfies: 3.1 g/cm 3 ⁇ PD ⁇ 3.5 g/cm 3 , with a preferred range of 3.2 g/cm 3 ⁇ PD ⁇ 3.5 g/cm 3 .
  • the compaction density PD of the positive pole piece is within the above range, the thickness of the positive pole piece formed after cold pressing is moderate, the energy density under the same capacity is relatively large, and the charge and discharge power is relatively high; at the same time, the value The range of PD can ensure that the positive pole piece has better processing performance.
  • PD is the compaction density of the positive pole piece.
  • the average particle diameter of the positive electrode active material I particles is 0.1 ⁇ m to 25 ⁇ m, preferably 3 ⁇ m to 16 ⁇ m. More preferably, when the positive electrode active material I is a single particle, the average particle diameter of the positive electrode active material I is preferably 3 ⁇ m-7 ⁇ m. When the positive electrode active material I is a secondary particle, the average particle diameter of the positive electrode active material I is preferably 6 ⁇ m to 16 ⁇ m.
  • the average particle size of the particles of the positive electrode active material II is 0.01 ⁇ m to 15 ⁇ m, preferably 2.5 ⁇ m to 7 ⁇ m.
  • the particle size distribution (D max- D min ) I of the positive active material I is smaller than the particle size distribution (D max- D min ) II of the positive active material II.
  • the positive electrode active material I is a single particle, and the positive electrode active material II includes fine powder particles of 100 nm to 1000 nm and secondary particles of 8 ⁇ m to 16 ⁇ m in diameter.
  • the positive active material I is a layered lithium nickel transition metal oxide
  • the layered lithium nickel transition metal oxide is selected from: Li x1 Ni (1-y1-z1-a1 Co y1) Mn z1 M1 a1 O 2 , Li x2 Ni (1-y2-z2-a2) Co y2 Al z2 M2 a2 O 2 , and one or more of the composite materials obtained by coating modification of the above materials, wherein 0.90 ⁇ x1 ⁇ 1.05, 0 ⁇ y1 ⁇ 0.2, 0 ⁇ z1 ⁇ 0.2, 0 ⁇ a1 ⁇ 0.05, M1 is selected from one or more of Ti, Al, Zr, Mg, Zn, Ba, Mo, B; 0.90 ⁇ x2 ⁇ 1.05, 0 ⁇ y2 ⁇ 0.1, 0 ⁇ z2 ⁇ 0.1, 0 ⁇ a2 ⁇ 0.05, M2 is selected from one or more of Ti, Mn, Zr, Mg, Zn, Ba, Mo, and B.
  • the layered lithium nickel transition metal oxides mentioned in this application include but are not limited to LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.5 Co 0.25 Mn 0.25 O 2 , LiNi 0.55 Co 0.15 Mn 0.3 O 2 , LiNi 0.55 Co 0.1 Mn 0.35 O 2 , LiNi 0.55 Co 0.05 Mn 0.4 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.65 Co 0.15 Mn 0.2 O 2 , LiNi 0.65 Co 0.12 Mn 0.23 O 2 , LiNi 0.65 Co 0.1 Mn 0.25 O 2 , LiNi 0.65 Co 0.05 Mn 0.3 O 2 , LiNi 0.7 Co 0.1 Mn 0.2 O 2 , LiNi 0.75 Co 0.1 Mn 0.15 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.85 Co 0.05 Mn 0.1 O 2 , LiNi 0.88 Co 0.05 M
  • the above substances can also be partially substituted and modified by doping elements M1 or M2
  • M1 is selected from one or more of Ti, Al, Zr, Mg, Zn, Ba, Mo, B
  • M2 is selected from Ti, Mn, Zr, Mg, Zn, Ba, Mo, B One or more of them.
  • the lithium-containing olivine-type phosphate-based positive electrode of the lithium ion battery of the first aspect of the present application is LiFe 1-x3-y3 Mn x3 M 'y3 PO 4, 0 ⁇ x3 ⁇ 1 , 0 ⁇ y3 ⁇ 0.1, 0 ⁇ x3+y3 ⁇ 1, M'is selected from one or more of transition metal elements other than Fe and Mn and non-transition metal elements.
  • the olivine-type lithium-containing phosphate is selected from one or more of LiFePO 4 , LiMnPO 4 , LiMn 1-x3 Fe x3 PO 4 , and 0 ⁇ x3 ⁇ 1.
  • the instantaneous output power of the lithium-ion battery of the present application is not less than 2W/Wh at 20% SOC.
  • the following is an exemplary description of the positive pole piece, negative pole piece, separator and electrolyte of the lithium ion battery of the present application.
  • the preparation method of the positive pole piece may include the following steps: after mixing the positive electrode active material I, the positive electrode active material II, the binder, and the conductive agent to form a slurry, Coated on the positive electrode current collector.
  • the positive active material layer may further include a conductive agent and a binder, wherein the type and content of the conductive agent and the binder are not specifically limited, and can be selected according to actual requirements.
  • the adhesive usually includes a fluorine-containing polyolefin-based adhesive. Compared with the fluorine-containing polyolefin-based adhesive, water is usually a good solvent, that is, the fluorine-containing polyolefin-based adhesive is usually It has good solubility in water.
  • the fluorine-containing polyolefin binder may include but not limited to polyvinylidene fluoride (PVDF), vinylidene fluoride copolymers or their modifications (for example, carboxylic acid, acrylic acid).
  • the mass percentage content of the binder may be due to the poor conductivity of the binder itself, so the amount of the binder cannot be too high.
  • the mass percentage of the binder in the positive electrode active material layer is less than or equal to 2 wt%, so as to obtain a lower pole piece impedance.
  • the conductive agent of the positive pole piece may be various conductive agents suitable for lithium ion batteries in the field, for example, may include but not limited to acetylene black, conductive carbon black, carbon fiber (VGCF), carbon nanotube (CNT), One or more combinations of Ketjen Black, etc.
  • the weight of the conductive agent may account for 1 wt% to 10 wt% of the total mass of the positive electrode material layer. More preferably, the weight ratio of the conductive agent to the positive electrode active material in the positive pole piece is greater than or equal to 1.5:95.5.
  • the type of the positive electrode current collector is not specifically limited, and can be selected according to actual needs.
  • the positive electrode current collector can usually be a layered body, the positive electrode current collector is usually a structure or part that can collect current, and the positive electrode current collector can be various in the field suitable for being used as a positive electrode current collector of a lithium ion battery.
  • the positive electrode current collector may include but is not limited to metal foil, and more specifically may include but not limited to nickel foil and aluminum foil.
  • the negative electrode sheet generally includes a negative electrode current collector and a negative electrode active material layer on the surface of the negative electrode current collector, the negative electrode active material layer includes a negative electrode active material, and the negative electrode active material is selected from Any of soft carbon, hard carbon, artificial graphite, natural graphite, silicon, silicon-oxygen compound, silicon-carbon composite, lithium titanate, or metal that can form an alloy with lithium.
  • the porosity of the negative pole piece satisfies 19% ⁇ P 2 ⁇ 25%, preferably 20% ⁇ P 2 ⁇ 24%.
  • the isolation film may be various materials suitable for lithium ion battery isolation films in the field, for example, may include but not limited to polyethylene, polypropylene, polyvinylidene fluoride, and aramid. , Polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester and one or more combinations of natural fibers.
  • Fig. 1 and Fig. 2 show a lithium-ion battery 5 with a square structure as an example.
  • the lithium ion battery can be assembled into a battery module, and the number of lithium ion batteries 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 battery module 4 as an example.
  • a plurality of lithium ion batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other manner. Furthermore, the plurality of lithium ion batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodating space, and a plurality of lithium ion batteries 5 are accommodated in the accommodating space.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • FIGS 4 and 5 show the battery pack 1 as an example. 4 and 5, the battery pack 1 may include a battery box and a plurality of battery modules 4 provided in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3.
  • the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4.
  • a plurality of battery modules 4 can be arranged in the battery box in any manner.
  • the application provides a positive electrode sheet for a lithium ion battery, including a positive electrode active material layer, and the positive electrode active material in the positive electrode active material layer includes a positive electrode active material I and a positive electrode active material II, the positive active material I is a layered lithium nickel transition metal oxide, and the positive active material II is an olivine-type lithium-containing phosphate,
  • the positive pole piece satisfies: 2.5 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 21, where,
  • A is the mass percentage of the positive electrode active material II in the total weight of the positive electrode active material
  • N is the number of the positive electrode active material I particles at the intersection of the length center line of the electrode body and the height center line of the electrode body along the thickness direction of the positive electrode sheet;
  • PD is the compacted density of the positive pole piece, in g/cm 3 ;
  • P 1 is the porosity of the positive pole piece.
  • the positive electrode active material I has a single particle morphology, 6 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 21, preferably 8 ⁇ N/( PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 19.
  • the positive electrode active material I has a secondary particle morphology, 2.5 ⁇ N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 9, preferably 3 ⁇ N/ (PD ⁇ (1-P 1 ) ⁇ (1-A)) ⁇ 8.
  • the lithium-ion battery when the positive pole piece satisfies the above relational expression, the lithium-ion battery can obtain a larger discharge current and discharge power at a low SOC, and can meet the instantaneous acceleration of the existing automobile at a low SOC.
  • the positive pole piece provided in this application is determined by reasonably setting the particle size, relative percentage content of the positive electrode active material I and the positive electrode active material II, the number of the positive electrode active material I particles at the center of the pole piece, and the compaction density and porosity of the pole piece. It can improve the instantaneous discharge power of the battery under low SOC and achieve good power performance.
  • the number N of the positive electrode active material I particles contained in the positive electrode active material layer is 6 to 55.
  • N is 6 to 40; more preferably, when the positive electrode active material I is a single particle, N is 20 to 40; when the positive electrode active material I is a secondary particle, N is 6 ⁇ 20.
  • the porosity of the overall positive electrode piece can be adjusted, and the transmission of lithium ions in the positive electrode active material I can be ensured, so that the positive electrode piece maintains a better charge. Discharge power.
  • the positive pole piece provided in the second aspect of the present application is the positive pole piece used in the lithium ion battery of the first aspect of the application. Therefore, the positive pole piece provided in the second aspect is the same as the positive pole of the lithium ion battery in the first aspect.
  • the composition parameters of the slices are the same in all directions, and will not be repeated here.
  • the present application provides a device that includes the lithium ion battery described in the first aspect of the present application, and the lithium ion battery serves as a power source for the device.
  • the device using the battery 5 is an electric vehicle.
  • the device using the battery 5 can be any electric vehicle other than electric vehicles (for example, electric buses, electric trams, electric bicycles, electric motorcycles, electric scooters, electric golf carts, electric trucks), Electric ships, electric tools, electronic equipment and energy storage systems.
  • the electric vehicle can be an electric pure electric vehicle, a hybrid electric vehicle, and a plug-in hybrid electric vehicle.
  • the device provided in the third aspect of the application may include the battery module 4 described in the first aspect of the application.
  • the device provided in the third aspect of the application may also include the device provided in the first aspect of the application. Mentioned battery pack 1.
  • This embodiment is a lithium ion battery, and its specific preparation process is as follows:
  • the proportion of LiFePO 4 in the positive electrode active material is denoted as A;
  • the prepared basic electrolyte is injected and packaged to obtain a lithium ion battery.
  • Examples 2-15 are respectively a lithium ion battery, and the differences from Example 1 are listed in Table 3.
  • the specific composition of the positive electrode active material of each example is shown in Table 1 and Table 2.
  • the parts not listed in Table 3 are the same as those in Example 1. Among them, N/(PD ⁇ (1-P 1 ) ⁇ (1-A)) is denoted as ⁇ .
  • Comparative Examples 1-3 are respectively a lithium ion battery, and the differences from Example 1 are listed in Table 3.
  • the specific composition of the positive active material of each comparative example is shown in Table 1 and Table 2.
  • the parts not listed in Table 3 are the same as those in Example 1.
  • the positive electrode active material II LiFePO 4
  • Comparative Example 3 the positive electrode active material II (LiFePO 4 ) was not added.
  • NCM532 is Li[Ni 0.5 Co 0.2 Mn 0.3 ]O 2 ,
  • NCM811 is Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 ,
  • NCM622 is Li[Ni 0.6 Co 0.2 Mn 0.2 ]O 2 .
  • the magnification is 1000-5000 times.
  • the ternary active material is Li[Ni 0.5 Co 0.2 Mn 0.3 ]O 2 , because the particles of the material are small, use 5000 times magnification to measure; when the ternary active material is Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 Because the material particles are relatively large, it is preferable to use 1000 times magnification for measurement.
  • the compaction density and porosity of the positive pole piece can optimize the transmission rate and charge and discharge power of lithium ions in the positive pole piece, thereby achieving the purpose of increasing the instantaneous discharge power of the battery at a low SOC.

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Abstract

一种锂离子电池(5)、用于锂离子电池(5)的正极极片及装置。所述锂离子电池(5)包括正极极片，所述正极极片包括正极集流体和设置于所述正极集流体至少一个表面的正极活性材料层，所述正极活性材料层中的正极活性材料包括正极活性物质I和正极活性物质II，所述正极活性物质I为层状锂镍过渡金属氧化物，所述正极活性物质II为橄榄石型含锂磷酸盐，所述正极极片满足：2.5≤N/(PD×(1-P1)×(1-A))≤21。所述锂离子电池正极极片的能量密度较高、锂离子的传输速率高，从而保证使用上述正极极片的锂离子电池的体积能量密度较高的同时，在低SOC状态下的瞬时放电功率得到有效提高。

Description

锂离子电池、用于锂离子电池的正极极片及装置 技术领域
本申请涉及电池领域，具体而言，涉及一种锂离子电池、用于锂离子电池的正极极片及装置。
背景技术
随着国家对环境保护的重视越来越大，新能源汽车产业也得到了国家的大力支持。新能源汽车市场份额正在逐年递增，不断取代传统燃油汽车。作为新能源汽车的三大件之首的电池技术也不断换代提升。电池的能量密度逐渐提高，容量逐渐提高，成本越来越低。但是作为衡量一款汽车性能好坏的关键因素之一的加速性能则对电池的充放电功率提出了很高的要求。
现阶段市场上量产的电池主要以磷酸铁锂体系和三元体系电池为主，这两种电池都有一个共同点就是在高SOC(电荷状态)下电池具有较高的放电功率，其功率能够支持汽车的瞬间加速，但是在低SOC状态下电池的瞬间输出功率却不能满足汽车在低电量时的瞬时加速。
针对以上电池在低SOC下功率过小的问题，现阶段普遍的改善方法有：1)减小活性物质在电芯集流体上的涂覆重量，以提高电池充放电最大电流，该方法的缺点是减小了活性物质在整个电芯重量的占比，从而降低了电芯的质量能量密度：2)选用动力学性能更好的活性物质，同时增加导电碳的含量以提高充放电最大电流，该方法的缺点是提高了电池的原料成本：3)选用高离子电导的电解液增加离子导通性以提高充放电最大电流，该方法的缺点是成本提高，同时在电池循环充放电过程中电解液容易被分解造成电池内部气压过大，容易引发安全事故。
发明内容
本申请的目的在于提供一种锂离子电池，以解决目前锂离子电池在低SOC状态下瞬间输出功率低的问题；并提供一种用于锂离子电池的正极极片及装置。
为达到上述目的，本申请采用的技术方案如下：
本申请的第一方面，提供一种锂离子电池，包括正极极片，所述正极极片包括正极集流体和设置于所述正极集流体至少一个表面的正极活性材料层，所述正极活性材料层中的正极活性材料包括正极活性物质I和正极活性物质II，所述正极活性物质I为层状锂镍过渡金属氧化物，所述正极活性物质II为橄榄石型含锂磷酸盐，
所述正极极片满足：2.5≤N/(PD×(1-P 1)×(1-A))≤21，
其中，A为所述正极活性物质II占所述正极活性材料总重量的质量百分比；
N为沿所述正极活性材料层的厚度方向，所述正极活性材料层所容纳的所述正极活性物质I颗粒的个数；
PD为所述正极极片的压实密度，单位为g/cm 3；
P 1为所述正极极片的孔隙率。
第二方面，本申请提供一种用于锂离子电池的正极极片，所述正极极片包括正极集流体和设置于所述正极集流体至少一个表面的正极活性材料层，所述正极活性材料层中的正极活性材料包括正极活性物质I和正极活性物质II，所述正极活性物质I为层状锂镍过渡金属氧化物，所述正极活性物质II为橄榄石型含锂磷酸盐，
所述正极极片满足：2.5≤N/(PD×(1-P 1)×(1-A))≤21，
其中，A为所述正极活性物质II占所述正极活性材料总重量的质量百分比；
N为沿所述正极活性材料层的厚度方向，所述正极活性材料层所容纳的所述正极活性物质I颗粒的个数；
PD为所述正极极片的压实密度，单位为g/cm 3；
P 1为所述正极极片的孔隙率。
本申请的第三方面，提供了一种装置，包括本申请的第一方面所述的锂离子电池，所述锂离子电池用作所述装置的电源。
与现有技术相比，本申请至少可以取得以下有益效果：
本申请提供的锂离子电池中，正极极片包括正极活性材料层，其中正极活性材料层包括正极活性物质I和正极活性物质II，正极活性物质I为层状锂镍过渡金属氧化物，正极活性物质II为橄榄石型含锂磷酸盐，上述正极极片满足2.5≤N/(PD×(1-P 1)×(1-A))≤21，当正极极片满足该关系式时，锂离子电池能够在低SOC下获得较大的放电电流和放电功率，尤其能够满足现有动力汽车对锂离子电池处于低SOC状态下的瞬时加速需求。
本申请提供的锂离子电池，通过合理设置正极活性材料中层状锂镍过渡金属氧化物和橄榄石型含锂磷酸盐的活性物质粒径分布、相对百分含量、正极极片层面各活性物质颗粒之间的间距、以及整个正极极片的压实密度和孔隙率，从而优化正极极片中锂离子的传输速率、能量密度和充放电功率等，进而达到在保证锂离子电池具有高体积能量密度的同时，提高电池在低SOC下的瞬时放电功率。
本申请的装置包括本申请所述的锂离子电池，因而至少具有与所述锂离子电池相同的优势。
附图说明
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图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，还可以根据这些附图获得其他的附图。
图1是锂离子电池的一实施方式的立体图；
图2是锂离子电池的一实施方式的分解图；
图3是电池模块的一实施方式的立体图；
图4是电池包的一实施方式的立体图；
图5是图4的分解图；
图6是锂离子电池作为电源的装置的一实施方式的示意图。
其中，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
51 壳体
52 电极组件
53 顶盖组件。
具体实施方式
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。
在本申请的第一方面，本申请提供了一种锂离子电池，包括正极极片，所述正极极片包括正极集流体和设置于所述正极集流体至少一个表面的正极活性材料层，所述正极活性材料层中的正极活性材料包括正极活性物质I和正极活性物质II，所述正极活性物质I为层状锂镍过渡金属氧化物，所述正极活性物质II为橄榄石型含锂磷酸盐，
所述正极极片满足：2.5≤N/(PD×(1-P 1)×(1-A))≤21，
其中，A为所述正极活性物质II占所述正极活性材料总重量的质量百分比；
N为为沿所述正极活性材料层的厚度方向，所述正极活性材料层所容纳的所述正极活性物质I颗粒的个数；
PD为所述正极极片的压实密度，单位为g/cm 3；
P 1为所述正极极片的孔隙率。
本申请提供的锂离子电池，通过合理设置正极活性材料中层状锂镍过渡金属氧化物和橄榄石型含锂磷酸盐的活性物质粒径分布、相对百分含量、正极极片层面各活性物质颗粒之间的间距、以及整个正极极片的压实密度和孔隙率，从而优化正极极片中锂离子的传输速率和充放电功率，进而达到提高电池在低SOC下的瞬时放电功率的目的。
本申请提供的锂离子电池中，正极极片层面低SOC下功率的输出特性与各活性物质颗粒之间的间距、正极极片的压实密度和孔隙率与正极活性物质I、正极活性物质II的种类、各自的颗粒形态、粒径分布，以及二者混合后整体的粒径分布状况密切相关。
作为本申请的一些优选实施方式，本申请中所述正极活性物质I为单颗粒形貌时，6≤N/(PD×(1-P 1)×(1-A))≤21，优选为8≤N/(PD×(1-P 1)×(1-A))≤19。
作为本申请的一些优选实施方式，本申请中所述正极活性物质I为二次颗粒形貌时，2.5≤N/(PD×(1-P 1)×(1-A))≤9，优选为3≤N/(PD×(1-P 1)×(1-A))≤8。
进一步地，沿所述正极活性材料层的厚度方向，所述正极活性材料层所容纳的所述正极活性物质I颗粒的个数N为6个～55个，优选为7个～40个。更优选地，所述正极活性物质I为单颗粒时，N为20个～40个；所述正极活性物质I为二次颗粒时，N为6个～20个。本申请中通过优化正极活性物质I颗粒N的取值，既可以调整正极极片整体的孔隙率，又可以保证锂离子在正极活性物质I中的传输，从而使正极极片维持较好的充放电功率。
具体的，所述N的取值范围包括但非限制性的例如可以为7个、10个、12个、15个、17个、20个、23个、25个、28个、30个、32个、35个、38个、40个、42个、45个、48个、50个、53个、55个。
本申请中，N为沿所述正极活性材料层的厚度方向，所述正极活性材料层所容纳的所述正极活性物质I颗粒的个数。
作为示例性说明，在计算N时中，对正极极片的任意10个位置，沿正极极片的厚度方向做断面，分别沿厚度方向计算排列的正极活性物质I的颗粒数记为N 1、N 2、N 3、······N 9、N 10，并计算得出平均值记为N，即在厚度方向，正极活性材料层容纳的正极活性物质I的平均颗粒数，由此计算出N的取值。
在测试N时，使用断面扫描电镜观察，放大倍率采用1000倍～5000倍。当正极活性物质I为单颗粒形貌时，由于该材料颗粒较小，优先使用5000倍率放大测量；当正极活性物质I为二次颗粒形貌时，由于该材料颗粒较大，优选使用1000倍率放大测量。
进一步地，所述正极活性物质II占所述正极活性材料总重量的质量百分比A满足：2％≤A≤40％，优选为10％≤A≤20％。本申请的正极活性材料中，所述正极活性物质II所占的比例A在上述范围内，对应的锂离子电池的低SOC充放电功率性能较好，单体电池的体积能量密度较高。
进一步地，所述正极极片的孔隙率P 1满足：19％≤P 1≤25％，优选范围20％≤P 1≤25％。本申请中，所述正极极片孔隙率可以采用孔隙率测试仪进行测试。当正极极片的孔隙率控制在上述范围内时，一方面可以保证正极极片中可装载的活性物质的相对含量较多、有利于提高电池的体积能量密度，同时，可以保证锂离子可以快速进入极片内部，使得使用该正极极片的锂离子电池的充放电功率较好。
进一步地，所述正极极片的压实密度PD满足：3.1g/cm 3≤PD≤3.5g/cm 3，优选范围3.2g/cm 3≤PD≤3.5g/cm 3。本申请中，正极极片的压实密度PD在上述范围内时，则冷压后形成的正极极片的厚度适中，相同容量 下的能量密度较大，充放电功率较高；同时，该数值范围的PD可以保证正极极片有较好的加工性能。
本申请中，PD为正极极片的压实密度。PD可以用如下测试方法测试得到：取面积为1540.25mm 2大小的圆形正极极片为基本单位，其中，两面涂覆有正极活性材料的正极极片的总重量为M，正极集流体的重量为B，正极集流体的厚度为T，铜箔/铝箔的厚度为μ，则PD＝(M-B)/(T-μ)/1540.25*1000。
进一步地，所述正极活性物质I颗粒的平均粒径为0.1μm～25μm，优选为3μm～16μm。更优选地，所述正极活性物质I为单颗粒时，所述正极活性物质I的平均粒径优选为3μm～7μm。所述正极活性物质I为二次颗粒时，所述正极活性物质I的平均粒径优选为6μm～16μm。
进一步地，所述正极活性物质II的颗粒的平均粒径为0.01μm～15μm，优选为2.5μm～7μm。
进一步优选地，所述正极活性物质I的粒径分布(D max-D min) I相比于所述正极活性物质II的粒径分布(D max-D min) II更小。更为优选地，所述正极活性物质I为单颗粒，所述正极活性物质II包括100nm～1000nm的微粉颗粒以及粒径为8μm～16μm的二次颗粒。采用上述粒径分布特征的正极活性物质I和正极活性物质II的混合物作为正极活性材料，既能实现高压实密度的正极极片，发挥正极活性物质I高能量密度的优势，又能发挥正极活性物质II在低电压下改善电池充放电功率的性能。
本申请中，所述正极活性物质I为层状锂镍过渡金属氧化物，所述层状锂镍过渡金属氧化物选自：Li x1Ni (1-y1-z1-a1Co y1)Mn z1M1 a1O 2、Li x2Ni (1-y2-z2-a2)Co y2Al z2M2 a2O 2、以及上述材料经包覆改性得到的复合材料中的一种或几种，其中，0.90≤x1≤1.05，0＜y1≤0.2，0＜z1≤0.2，0≤a1≤0.05，M1选自Ti、Al、Zr、Mg、Zn、Ba、Mo、B中的一种或几种；0.90≤x2≤1.05，0＜y2≤0.1，0＜z2≤0.1，0≤a2≤0.05，M2选自Ti、Mn、Zr、Mg、Zn、Ba、Mo、B中的一种或几种。
进一步优选地，0＜y1+z1+a1≤0.4；0＜y2+z2+a2≤0.4。
具体的，本申请中所述层状锂镍过渡金属氧化物包括但不限于LiNi 0.5Co 0.2Mn 0.3O 2、LiNi 0.5Co 0.25Mn 0.25O 2、LiNi 0.55Co 0.15Mn 0.3O 2、LiNi 0.55Co 0.1Mn 0.35O 2、LiNi 0.55Co 0.05Mn 0.4O 2、LiNi 0.6Co 0.2Mn 0.2O 2、LiNi 0.65Co 0.15Mn 0.2O 2、LiNi 0.65Co 0.12Mn 0.23O 2、LiNi 0.65Co 0.1Mn 0.25O 2、LiNi 0.65Co 0.05Mn 0.3O 2、LiNi 0.7Co 0.1Mn 0.2O 2、LiNi 0.75Co 0.1Mn 0.15O 2、LiNi 0.8Co 0.1Mn 0.1O 2、LiNi 0.85Co 0.05Mn 0.1O 2、LiNi 0.88Co 0.05Mn 0.07O 2、LiNi 0.9Co 0.05Mn 0.05O 2、LiNi 0.92Co 0.03Mn 0.05O 2、LiNi 0.95Co 0.02Mn 0.03O 2等，也可以为上述物质经过掺杂元素M1或M2进行部分取代改性后的物质，其中，M1选自Ti、Al、Zr、Mg、Zn、Ba、Mo、B中的一种或几种，M2选自Ti、Mn、Zr、Mg、Zn、Ba、Mo、B中的一种或几种。
在根据本申请第一方面所述锂离子电池的正极极片中，所述橄榄石型含锂磷酸盐的通式为LiFe 1-x3-y3Mn x3M’ y3PO 4，0≤x3≤1，0≤y3≤0.1，0≤x3+y3≤1，M’选自除Fe、Mn外的过渡金属元素以及非过渡金属元素中的一种或几种。
优选地，所述橄榄石型含锂磷酸盐选自LiFePO 4、LiMnPO 4、LiMn 1-x3Fe x3PO 4中的一种或几种，0＜x3＜1。
通过测试可得，本申请的锂离子电池在20％SOC下瞬间输出功率不低于2W/Wh。
下面对本申请锂离子电池的正极极片、负极极片、隔膜和电解液做示例性说明。
本领域技术人员可选择合适的方法制备正极极片，例如，正极极片的制备方法可以包括如下步骤：将正极活性物质I、正极活性物质II、粘结剂、导电剂混合形成浆料后，涂布于正极集流体上。
在正极极片中，所述正极活性物质层还可包括导电剂以及粘结剂，其中导电剂以及粘结剂的种类和含量不受具体的限制，可根据实际需求进行选择。所述粘结剂通常包括含氟聚烯烃类粘结剂，相对于所述含氟聚烯烃类粘结剂来说， 水通常是良溶剂，即所述含氟聚烯烃类粘结剂通常在水中具有良好的溶解性，例如，所述含氟聚烯烃类粘结剂可以是包括但不限于聚偏氟乙烯(PVDF)、偏氟乙烯共聚物或它们的改性(例如，羧酸、丙烯酸、丙烯腈等改性)衍生物等。在所述正极材料层中，粘结剂的质量百分比含量可以是由于粘结剂本身的导电性较差，因此粘结剂的用量不能过高。优选地，正极活性物质层中粘结剂的质量百分含量小于等于2wt％，以获得较低的极片阻抗。所述正极极片的导电剂可以是本领域各种适用于锂离子电池的导电剂，例如，可以是包括但不限于乙炔黑、导电炭黑、碳纤维(VGCF)、碳纳米管(CNT)、科琴黑等中的一种或多种的组合。所述导电剂的重量可以占正极材料层总质量的1wt％～10wt％。更优选地，正极极片中导电剂与正极活性材料的重量比大于等于1.5:95.5。所述正极集流体的种类也不受具体的限制，可根据实际需求进行选择。本申请中，所述正极集流体通常可以为层体，所述正极集流体通常是可以汇集电流的结构或零件，所述正极集流体可以是本领域各种适用于作为锂离子电池正极集流体的材料，例如，所述正极集流体可以是包括但不限于金属箔，更具体可以是包括但不限于镍箔、铝箔。
在本申请的锂离子电池中，所述负极极片通常包括负极集流体和位于负极集流体表面的负极活性材料层，所述负极活性材料层中包括负极活性材料，所述负极活性材料选自软碳、硬碳、人造石墨、天然石墨、硅、硅氧化合物、硅碳复合物、钛酸锂或能与锂形成合金的金属中的任一种。
进一步地，所述负极极片的孔隙率满足19％≤P 2≤25％，优选满足20％≤P 2≤24％。
在本申请的锂离子电池中，所述隔离膜可以是本领域各种适用于锂离子电池隔离膜的材料，例如，可以是包括但不限于聚乙烯、聚丙烯、聚偏氟乙烯、芳纶、聚对苯二甲酸乙二醇酯、聚四氟乙烯、聚丙烯腈、聚酰亚胺，聚酰胺、聚酯和天然纤维中的一种或多种的组合。
本申请对锂离子电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。如图1和图2是作为一个示例的方形结构的锂离子电池5。
在一些实施例中，锂离子电池可以组装成电池模块，电池模块所含锂离子电池的数量可以为多个，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。参照图3，在电池模块4中，多个锂离子电池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锂离子电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的壳体，多个锂离子电池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。参照图4和图5，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体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电池箱中。
在本申请的第二方面，本申请提供了一种用于锂离子电池的正极极片，包括正极活性材料层，所述正极活性材料层中的正极活性材料包括正极活性物质I和正极活性物质II，所述正极活性物质I为层状锂镍过渡金属氧化物，所述正极活性物质II为橄榄石型含锂磷酸盐，
所述正极极片满足：2.5≤N/(PD×(1-P 1)×(1-A))≤21，其中，
A为所述正极活性物质II占所述正极活性材料总重量的质量百分比；
N为在所述电极主体的长度中心线与所述电极主体的高度中心线的交叉处，沿所述正极极片厚度方向，所述正极活性物质I颗粒的个数；
PD为所述正极极片的压实密度，单位为g/cm 3；
P 1为所述正极极片的孔隙率。
进一步地，本申请中，所述正极活性物质I为单颗粒形貌时，6≤N/(PD×(1-P 1)×(1-A))≤21，优选为8≤N/(PD×(1-P 1)×(1-A))≤19。
进一步地，本申请中，所述正极活性物质I为二次颗粒形貌时，2.5≤N/(PD×(1-P 1)×(1-A))≤9，优选为3≤N/(PD×(1-P 1)×(1-A))≤8。
本申请中，当正极极片满足上述关系式时，锂离子电池能够在低SOC下获得较大的放电电流和放电功率，能够满足现有汽车低SOC下的瞬时加速。本申请提供的正极极片，通过合理设置正极活性物质I和正极活性物质II的颗粒尺寸、相对百分含量、极片中心位置正极活性物质I颗粒个数、以及极片的压实密度和孔隙率，从而提高电池低SOC下的瞬时放电功率、实现良好的功率性能。
本申请中，沿所述正极活性材料层的厚度方向，所述正极活性材料层所容纳的所述正极活性物质I颗粒的个数N为6个～55个。优选的，N为6个～40个；更优选的，所述正极活性物质I为单颗粒时，N为20个～40个；所述正极活性物质I为二次颗粒时，N为6个～20个。本申请中通过优化正极活性物质I颗粒N的取值，既可以调整正极极片整体的孔隙率，又可以保证锂离子在正极活性物质I中的传输，从而使正极极片维持较好的充放电功率。
具体地，本申请第二方面提供的正极极片为本申请第一方面锂离子电池中所用的正极极片，因此，第二方面提供的正极极片与第一方面锂离子电池中的正极极片的各向组成参数均相同，在此不再做重复赘述。
在本申请的第三方面，本申请提供了一种装置，所述装置包括本申请第一方面所述的锂离子电池，所述锂离子电池作为所述装置的电源。
在图6中，采用电池5的装置为电动汽车。当然不限于此，采用电池5的装置可以为除电动汽车外的任何电动车辆(例如电动大巴、电动有轨电车、电动自行车、电动摩托车、电动踏板车、电动高尔夫球车、电动卡车)、电动船 舶、电动工具、电子设备及储能***。电动汽车可以为电动纯电动车、混合动力电动车、插电式混合动力电动车。当然，依据实际使用形式，本申请第三方面提供的装置可包括本申请的第一方面所述的电池模块4，当然，本申请第三方面提供的装置也可包括本申请的第一方面所述的电池包1。
下面将结合实施例和对比例对本申请做进一步详细说明。
实施例1
本实施例是一种锂离子电池，其具体制备过程如下：
1)正极极片制备：在200L搅拌罐中按重量占比92.3％：3％：2.3％：1.1％分别加入正极活性物质I-1(NCM523)、正极活性物质II-1(LiFePO 4)、导电剂乙炔黑和粘结剂聚偏二氟乙烯(PVDF)(正极活性物质I-1及II-2的具体参数见表1和表2)，以800转/分钟的分散速度搅拌15分钟，然后再在N-甲基吡咯烷酮溶剂体系中以1200转/分钟的速度分散搅拌220分钟，最后调节浆料粘度在8900mPa·s。将充分搅拌混合均匀后的浆料，涂覆于厚度为13μm的Al箔上烘干、冷压，最后得到正极极片；
其中，LiFePO 4在正极活性材料中的占比记为A；
2)以PE多孔聚合薄膜作为隔离膜；
3)负极极片制备：在200L搅拌罐中按重量占比96.2％：1.2％：0.8％：1.8％分别加入负极石墨粉料、分散剂、导电剂和粘结剂以800转/分钟的分散速度干混搅拌15分钟，然后再加入一定量的去离子水，以1000转/分钟的速度分散搅拌60分钟，最后调节浆料粘度在10000mPa·s。将充分搅拌混合均匀后的浆料，涂覆于厚度为6μm的铜箔上烘干、冷压，最后得到负极极片，负极极片的孔隙率为20％；
4)将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正极极片和负极极片中间起到隔离的作用，并卷绕得到裸电芯，将裸电芯置于外包装中，注入配好的基础电解液并封装，得到锂离子电池。
实施例2-15
实施例2-15分别是一种锂离子电池，其与实施例1的不同之处列于表3中，各实施例的正极活性物质具体组成原料参见表1和表2。表3中未列出部分与实施例1相同。其中，N/(PD×(1-P 1)×(1-A))记为α。
对比例1-3
对比例1-3分别是一种锂离子电池，其与实施例1的不同之处列于表3中，各对比例的正极活性物质具体组成原料参见表1和表2。表3中未列出部分与实施例1相同。其中，对比例3中未添加正极活性物质II(LiFePO 4)。
表1
Figure PCTCN2019123338-appb-000001
注：NCM532为Li[Ni 0.5Co 0.2Mn 0.3]O 2，
NCM811为Li[Ni 0.8Co 0.1Mn 0.1]O 2，
NCM622为Li[Ni 0.6Co 0.2Mn 0.2]O 2。
表2
Figure PCTCN2019123338-appb-000002
Figure PCTCN2019123338-appb-000003
正极极片参数测定
1、正极活性材料层的厚度方向，正极活性材料层所容纳的所述正极活性物质I颗粒的个数N的测量方法
在测量正极活性物质I的个数N时，使用断层扫描电镜观察正极极片的厚度方向的断面，放大倍率采用1000倍-5000倍。当三元活性材料为Li[Ni 0.5Co 0.2Mn 0.3]O 2时，由于该材料颗粒较小，使用5000倍率放大测量；当三元活性材料为Li[Ni 0.8Co 0.1Mn 0.1]O 2时，由于该材料颗粒较大，优选使用1000倍率放大测量。
该测试方法中，对正极极片的任意10个位置，沿正极极片的厚度方向做断面，分别沿厚度方向计算排列的正极活性物质I的颗粒数记为N 1、N 2、N 3、······N 9、N 10，并计算得出平均值记为N，即在厚度方向，正极活性材料层容纳的正极活性物质I的平均颗粒数，由此计算出N的取值。
2、压实密度PD的测试方法
取面积为1540.25mm 2大小的圆形正极极片为基本单位，其中，两面涂覆有正极活性材料的正极极片的总重量为M，正极集流体的重量为B，正极集流体的厚度为T，铜箔/铝箔的厚度为μ，则PD＝(M-B)/(T-μ)/1540.25*1000。
3、孔隙率的测试方法
将极片冲切成直径≤16mm的小圆片，记录小圆片的厚度；然后利用孔隙率测试仪进行测试，得到极片的孔隙率。
表3
Figure PCTCN2019123338-appb-000004
锂离子电池性能测试：
1、电池容量测试：
(1)定义电芯标称容量为C(Ah)，电池电压范围为电池设计的电压上限(Umax)和电压下限(Umix)；
(2)将电池正负极与充放电机正负极链接，放入25℃恒温箱静置2小时；
(3)用1/3C电流恒流放电至下限电压Umix，静置1小时，然后以1/3C开始恒流恒压充电至电池上限电压Umax，静置1小时；
(4)用1/3电流给电池放电，使电池电压由Umax放电到Umix，此过程放出的容量标称为电池容量C0。
2、能量密度测试：
(1)将电池按照容量测试方法测试出电池由满充状态放电到电压下限时所释放出来的能量；
(2)用电池满放的能量除以电池的实际重量，即为此电池能量密度。
3、5％SOC下的放电功率：
(1)按照容量测试方法测出电池实际容量C0；
(2)将电池满充后，按照1/3C0电流将电池中的能量放出95％，此时电池状态为95％SOC。此时的电芯按照放电电流由小到大尝试，直到10s放电正好达到电池下线电压停止，此时测试出来的放电功率为此电池5％SOC下的放电功率。
采用上述方法分别测试实施例1-15和对比例1-3的锂离子电池的容量、能量密度和5％SOC下的放电功率。测试结果列于表4。
表4
Figure PCTCN2019123338-appb-000005
Figure PCTCN2019123338-appb-000006
从实施例1～15及对比例1～3中可以发现：正极极片层面低SOC下功率的输出特性与各活性物质颗粒之间的间距、正极极片的压实密度和孔隙率与正极活性物质I、正极活性物质II的种类、各自的颗粒形态、粒径分布，以及二者混合后整体的粒径分布状况密切相关。通过合理设置正极活性材料中层状锂镍过渡金属氧化物和橄榄石型含锂磷酸盐的活性物质粒径分布、相对百分含量、正极极片层面各活性物质颗粒之间的间距、以及整个正极极片的压实密度和孔隙率，从而优化正极极片中锂离子的传输速率和充放电功率，进而达到提高电池在低SOC下的瞬时放电功率的目的。
尽管已用具体实施例来说明和描述了本申请，然而应意识到，在不背离本申请的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本申请范围内的所有这些变化和修改。

Claims (13)

  1. 一种锂离子电池，包括正极极片，所述正极极片包括正极集流体和设置于所述正极集流体至少一个表面的正极活性材料层，
    所述正极活性材料层中的正极活性材料包括正极活性物质I和正极活性物质II，所述正极活性物质I为层状锂镍过渡金属氧化物，所述正极活性物质II为橄榄石型含锂磷酸盐，
    所述正极极片满足：2.5≤N/(PD×(1-P 1)×(1-A))≤21，
    其中，A为所述正极活性物质II占所述正极活性材料总重量的质量百分比；
    N为沿所述正极活性材料层的厚度方向，所述正极活性材料层所容纳的所述正极活性物质I颗粒的个数；
    PD为所述正极极片的压实密度，单位为g/cm 3；
    P 1为所述正极极片的孔隙率。
  2. 根据权利要求1所述的锂离子电池，其特征在于，
    所述正极活性物质I为单颗粒形貌时，6≤N/(PD×(1-P 1)×(1-A))≤21，优选为8≤N/(PD×(1-P 1)×(1-A))≤19；
  3. 根据权利要求1所述的锂离子电池，其特征在于，
    所述正极活性物质I为二次颗粒形貌时，2.5≤N/(PD×(1-P 1)×(1-A))≤9，优选为3≤N/(PD×(1-P 1)×(1-A))≤8。
  4. 根据权利要求1～3中任一项所述的锂离子电池，其特征在于，所述正极活性物质I的颗粒个数N为6个～55个，优选为6个～40个。
  5. 根据权利要求1～3中任一项所述的锂离子电池，其特征在于，所述正极活性物质II占所述正极活性材料总重量的质量百分比A满足：2％≤A≤40％，优选为10％≤A≤20％。
  6. 根据权利要求1～3中任一项所述的锂离子电池，其特征在于，所述正极极片的孔隙率P 1满足：19％≤P 1≤25％，优选范围20％≤P 1≤25％。
  7. 根据权利要求1～3中任一项所述的锂离子电池，其特征在于，所述正极极片的压实密度PD满足：3.1g/cm 3≤PD≤3.5g/cm 3，优选范围3.2g/cm 3≤PD≤3.5g/cm 3。
  8. 根据权利要求1～7中任一项所述的锂离子电池，其特征在于，所述正极活性物质I颗粒的平均粒径为0.1μm～25μm，优选为3μm～16μm，
    更优选地，所述正极活性物质I为单颗粒时，所述正极活性物质I的平均粒径优选为3μm～7μm；所述正极活性物质I为二次颗粒时，所述正极活性物质I的平均粒径优选为6μm～16μm；和/或，
    所述正极活性物质II的颗粒的平均粒径为0.01μm～15μm，优选为2.5μm～7μm。
  9. 根据权利要求1～8任一项所述的锂离子电池，其特征在于，
    所述层状锂镍过渡金属氧化物选自：Li x1Ni (1-y1-z1-a1)Co y1Mn z1M1 a1O 2、Li x2Ni (1-y2-z2-a2)Co y2Al z2M2 a2O 2、以及上述材料经包覆改性得到的复合材料中的一种或几种，其中，0.90≤x1≤1.05，0＜y1≤0.2，0＜z1≤0.2，0≤a1≤0.05，M1选自Ti、Al、Zr、Mg、Zn、Ba、Mo、B中的一种或几种；0.90≤x2≤1.05，0＜y2≤0.1，0＜z2≤0.1，0≤a2≤0.05，M2选自Ti、Mn、Zr、Mg、Zn、Ba、Mo、B中的一种或几种；
    优选地，0＜y1+z1+a1≤0.4；0＜y2+z2+a2≤0.4。
  10. 根据权利要求1～8任一项所述的锂离子电池，其特征在于，
    所述橄榄石型含锂磷酸盐的通式为LiFe (1-x3-y3)Mn x3M’ y3PO 4，0≤x3≤1，0≤y3≤0.1，M’选自除Fe、Mn外的过渡金属元素以及非过渡金属元素中的一种或几种；
    优选地，所述橄榄石型含锂磷酸盐选自LiFePO 4、LiMnPO 4、LiMn 1-x3Fe x3PO 4、LiV 1-x3Fe x3PO 4中的一种或几种，0＜x3＜1。
  11. 根据权利要求1～10任一项所述的锂离子电池，其特征在于，所述负极极片中的负极活性材料选自软碳、硬碳、人造石墨、天然石墨、硅、硅氧化合物、硅碳复合物、钛酸锂或能与锂形成合金的金属中的一种或多种。
  12. 一种用于锂离子电池的正极极片，其特征在于，所述正极极片包括正极集流体和设置于所述正极集流体至少一个表面的正极活性材料层，所述正极活性材料层中的正极活性材料包括正极活性物质I和正极活性物质II，所述正极活性物质I为层状锂镍过渡金属氧化物，所述正极活性物质II为橄榄石型含锂磷酸盐，
    所述正极极片满足：2.5≤N/(PD×(1-P 1)×(1-A))≤21，
    其中，A为所述正极活性物质II占所述正极活性材料总重量的质量百分比；
    N为沿所述正极活性材料层的厚度方向，所述正极活性材料层所容纳的所述正极活性物质I颗粒的个数；
    PD为所述正极极片的压实密度，单位为g/cm 3；
    P 1为所述正极极片的孔隙率。
  13. 一种装置，其特征在于，包括根据权利要求1～11中任一项所述的锂离子电池，所述锂离子电池用作所述装置的电源。
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