WO2021057457A1 - 钠离子电池用正极活性材料、由该活性材料制成的钠离子电池、电池模块、电池包及装置 - Google Patents

钠离子电池用正极活性材料、由该活性材料制成的钠离子电池、电池模块、电池包及装置 Download PDF

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WO2021057457A1
WO2021057457A1 PCT/CN2020/113822 CN2020113822W WO2021057457A1 WO 2021057457 A1 WO2021057457 A1 WO 2021057457A1 CN 2020113822 W CN2020113822 W CN 2020113822W WO 2021057457 A1 WO2021057457 A1 WO 2021057457A1
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active material
sodium ion
positive electrode
ion battery
electrode active
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English (en)
French (fr)
Inventor
黄丽婷
郭永胜
梁成都
兰加佃
林文光
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to EP20867772.4A priority Critical patent/EP3972016B1/en
Priority to EP24206452.5A priority patent/EP4559876A3/en
Publication of WO2021057457A1 publication Critical patent/WO2021057457A1/zh
Priority to US17/563,101 priority patent/US20220123299A1/en
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Priority to US19/192,309 priority patent/US20250260008A1/en
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    • 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
    • H01M4/50—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
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    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C01G53/502—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt
    • C01G53/504—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
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    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C01G53/51—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing sodium
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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    • 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
    • H01M50/244—Secondary casings; Racks; Suspension devices; Carrying devices; Holders characterised by their mounting method
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    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/249—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for aircraft or vehicles, e.g. cars or trains
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    • H01M2004/028—Positive electrodes
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    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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    • Y02T90/12—Electric charging stations

Definitions

  • the application belongs to the field of electrochemistry, and relates to a positive electrode active material for sodium ion batteries, in particular to a high voltage-resistant positive electrode active material for sodium ion batteries. This application also relates to sodium ion batteries, battery modules, battery packs and devices made of the above-mentioned positive electrode active materials.
  • cathode material Similar to lithium-ion batteries, the key factor restricting the performance of sodium-ion batteries is its cathode material.
  • cathode materials that have been widely studied, such as oxides, fluorides, sulfides, phosphates, pyrophosphates, metal organic frameworks/metal hexacyanides, and organic compounds, transition metal oxide cathode materials with a layered structure Due to its higher theoretical capacity, higher density, lower cost, and ease of material preparation, it has received extensive attention and has become a potential cathode material for sodium ion batteries.
  • the first aspect of the present application provides a positive electrode active material for a sodium ion battery, which mainly comprises an O3 phase layered metal oxide, and the O3 phase layered metal oxide has the following molecular formula:
  • the metal cation is selected from at least one of Li + , Cu 2+ , Zn 2+ , Co 2+ and Ti 4+.
  • the O3 phase layered metal oxide doped with specific metal cations has high structural stability, and can not only maintain a better cycle when applied at high voltages Performance, but also able to stably exert electrical performance.
  • the ratio of /I 104 is O3 phase layered metal oxide, the structure of the material is better, and the bond of metal-oxygen (MO) is stronger.
  • the above-mentioned O3 layered metal oxide has a better crystalline structure, and its space group is The ratio of the unit cell parameter c to the unit cell parameter a is relatively large for the hexagonal crystal system of, the material has excellent crystalline properties and has the best layered structure.
  • the metal oxide with such a structure when used at a higher voltage, can achieve better cycle performance, and at the same time can stably exert its electrical performance.
  • the O3 phase layered metal oxide has I(003)/I(104) ⁇ 0.62 in the X-ray diffraction spectrum, which may be between Between 0.67 and 1.5, where I(003) represents the peak intensity of the (003) crystal plane of the O3 phase layered metal oxide, I(104) represents the peak intensity of the (104) crystal plane of the O3 layered metal oxide, and I (003)/I(104) reflects the degree of mixing of sodium metal cations in the O3 phase layered metal oxide.
  • TM-O transition metal of the O3 phase layered metal oxide and oxygen
  • the O3 phase layered metal oxide is in the space group In the hexagonal crystal system, the ratio of the unit cell parameter c to the unit cell parameter a is ⁇ 5, optional ⁇ 5.5. As a result, the crystallinity of the O3 phase layered metal oxide is enhanced.
  • the O3 phase layered metal oxide has I(003)/I(104) ⁇ 0.62 in the X-ray diffraction spectrum. Between 0.67 and 1.5, and the O3 phase layered metal oxide is in the space group In the hexagonal crystal system, the ratio of the unit cell parameter c to the unit cell parameter a is ⁇ 5, optional ⁇ 5.5.
  • O3 phase layered metal oxides have particularly excellent structural stability, and thus exhibit particularly excellent electrical and dynamic properties when applied under high voltage.
  • the primary particles of the O3 phase layered metal oxide have a plate-like structure.
  • the obtained positive electrode active material has ideal structural stability and electrical properties.
  • the grain size of the primary particles is between 0.05 micrometers and 15 micrometers, and optionally between 0.1 micrometers and 5 micrometers.
  • the obtained positive electrode active material has ideal structural stability and electrical properties.
  • the compaction density of the positive electrode active material under a pressure of 8 tons is between 1.5 g/cm 3 and 4.5 g/cm 3 , which can be The choice is between 2.5g/cm 3 and 4g/cm 3 .
  • the obtained positive electrode active material has ideal structural stability and electrical properties.
  • the positive electrode active material is obtained by: i) In the presence of a complexing agent and a precipitating agent, a co-precipitation method is used to make Ni Source and Mn source are co-precipitated to obtain a nickel-manganese metal salt precursor, and ii) the nickel-manganese metal salt precursor obtained in step i) is solid-phase sintered with the Na source, Fe source, and M metal source to obtain O3 phase layered metal oxide cathode active material.
  • the sintering is performed at a temperature of 850-920°C for 15-25 hours.
  • the sintering is at a temperature of 850-920°C, optionally at a temperature of 890-910°C, and more optionally at a temperature of 895-905°C. It can be carried out at a temperature of 900°C.
  • a positive electrode active material having suitable crystalline properties is obtained.
  • the sintering is performed for 15-25 hours, optionally for 17-22 hours, more optionally for 19-21 hours, and most optionally for 20 hours. hour.
  • a positive electrode active material with excellent electrochemical performance is obtained.
  • the second aspect of the present application provides a sodium ion battery, which includes a positive pole piece, a negative pole piece, a separator spaced between the positive pole piece and the negative pole piece, and an electrolyte.
  • a current collector and a positive electrode active material layer provided on at least one side of the positive electrode current collector, wherein the positive electrode active material is a positive electrode active material according to the present application, and the battery has a charge cut-off voltage of 4.2V or higher.
  • the battery has a first discharge specific capacity of 120mAh/g at a voltage of 2.0-4.2V and a capacity of 87% or higher after 100 cycles at 1C Retention rate.
  • the third aspect of the present application provides a sodium ion battery, which includes a positive pole piece, a negative pole piece, a separator separated between the positive pole piece and the negative pole piece, and an electrolyte.
  • the positive pole piece includes a positive electrode collector.
  • a fluid and a positive electrode active material layer provided on at least one side of the positive electrode current collector, wherein the positive electrode active material is a positive electrode active material according to the present application, and the battery has a charge cut-off voltage of 4.5V or higher.
  • the battery has a first discharge specific capacity of 150mAh/g at a voltage of 2.0-4.5V and a capacity of 80% or higher after 100 cycles at 1C Retention rate.
  • the fourth aspect of the present application provides a battery module, which includes the sodium ion battery described in the second or third aspect of the present application.
  • a fifth aspect of the present application provides a battery pack, which includes the battery module described in the fourth aspect of the present application.
  • the sixth aspect of the present application provides a device, which includes the sodium ion battery according to the second or third aspect of the present application, and the sodium ion battery is used as a power source or an energy storage unit of the device; optional
  • the device includes electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, electric ships, and energy storage systems.
  • the battery module, battery pack, and device of the present application include the sodium ion battery provided in the present application, and thus have at least the same advantages as the sodium ion battery.
  • any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range.
  • every point or single value between the end points of the range is included in the range. Therefore, each point or single numerical value can be used as its own lower limit or upper limit, combined with any other point or single numerical value, or combined with other lower or upper limits to form an unspecified range.
  • I(003)/I(104) is used to reflect the degree of mixing of sodium metal cations in O3 phase layered metal oxides, where I(003) represents the positive electrode The peak intensity of the active material on the (003) crystal plane, and I(104) represents the peak intensity on the (104) crystal plane.
  • I(003)/I(104) the higher the mixing degree of sodium metal cations in the O3 phase layered metal oxide, which means the higher the structural order of the O3 phase layered metal oxide. The more stable the structure.
  • the ratio of the unit cell parameter c to the unit cell parameter a is used to characterize the crystal structure of the O3 phase layered metal oxide.
  • the material is considered to have good crystallization and a layered structure.
  • the larger the ratio the higher the proportion of the layered structure in the material, and the better the layered structure formed.
  • primary particles refer to crystalline particles of the O3-phase layered metal oxide, which are different from particles (secondary particles) formed after agglomeration of crystalline particles.
  • Fig. 1 is an X-ray derived spectrum of a cathode active material for a sodium ion battery using Example 5 of the present application.
  • FIG. 2 is the first charge and discharge curve of the button battery made of the positive electrode active material for the sodium ion battery of Example 5 of the present application under different voltages.
  • FIG. 3 shows the cycle performance of a button cell made of the positive electrode active material for a sodium ion battery of Example 5 of the present application under different voltages.
  • Fig. 4 is a perspective view of an embodiment of a sodium ion battery.
  • Fig. 5 is an exploded view of Fig. 4.
  • Fig. 6 is a perspective view of an embodiment of a battery module.
  • Fig. 7 is a perspective view of an embodiment of a battery pack.
  • Fig. 8 is an exploded view of Fig. 7.
  • Fig. 9 is a schematic diagram of an embodiment of a device using a sodium ion battery as a power source.
  • this application provides a positive electrode active material for sodium ion batteries, which mainly comprises O3 phase layered metal oxide, and the O3 phase layered metal oxide has the following molecular formula:
  • oxides with a layered structure are mainly used as positive electrode active materials.
  • the above metals have great advantages in terms of specific capacity and specific energy, and are considered to be very potential cathode materials for sodium ion batteries.
  • there is no suitable O3 phase layered transition metal oxide cathode material that still has high specific capacity and long life at an acceptable cost.
  • the positive electrode active material for a sodium ion battery mainly includes an O3 phase layered metal oxide.
  • the O3 phase layered metal oxide occupies the main part of the positive electrode active material.
  • the positive electrode active material for sodium ion batteries contains 90 wt% or more of the O3 phase layered metal oxide relative to the total weight of the positive electrode active material, and optionally 95 wt% or more of the O3 phase layer
  • the metal oxide may be 98 wt% or higher O3 phase layered metal oxide, and 99 wt% or higher O3 phase layered metal oxide may be more selected.
  • the cathode active material for a sodium ion battery is composed of an O3 phase layered metal oxide.
  • the inventor of the present application surprisingly found that in the positive electrode active material for sodium ion batteries according to the present application, the O3 phase layered metal oxide doped with specific metal cations has a higher structural stability, when under high voltage In application, it can not only exert its electrical performance stably, but also obtain significantly improved cycle performance. Without being bound by any theory, the applicant speculates that the reason is that after a specific type of metal element is doped with modified O3 phase sodium nickel manganese iron oxide, it can effectively inhibit the material from being in the high voltage range (for example, >4.1V)
  • the irreversible phase transition (P3-P3') ensures the structural stability of the material during charge and discharge, thereby achieving a better balance between capacity and cycle performance.
  • the irreversible phase transition (P3-P3') in the high voltage section is mainly caused by the JT effect of Ni 3+.
  • the doped metal enhances the interaction force between the transition metal and oxygen (TM-O), especially the interaction force between nickel and oxygen (Ni-O), which can be effective To inhibit the JT effect of Ni 3+ , so as to achieve the purpose of inhibiting the irreversible phase transition in the high voltage region.
  • the metal cation suitable for doping the O3 phase layered metal oxide is selected from at least one of Li + , Cu 2+ , Zn 2+ , Co 2+ , and Ti 4+.
  • the metal cation particularly suitable for doping the O3 phase layered metal oxide is Li + .
  • the doping of these specific types of metal cations is very important to improve the structural stability of metal oxides.
  • the inventor of the present application surprisingly found that the O3 phase layered metal oxide doped with these specific kinds of metal cations is compared with other metal cations (such as Mg 2+ ) doped with the O3 phase layered metal as disclosed in the related art. Oxides have improved structural stability. As a result, the O3 phase layered metal oxides obtained according to the present application show significantly better electrical and dynamic properties when applied under high voltage.
  • the O3 phase layered metal oxide has I(003)/I(104) ⁇ 0.62 in the X-ray diffraction spectrum, where I(003) represents the ( 003) crystal plane peak intensity, I(104) represents the (104) crystal plane peak intensity of the O3 phase layered metal oxide, I(003)/I(104) reflects the sodium metal cation in the O3 phase layered metal oxide The degree of mixing.
  • the I(003)/I(104) of the O3 phase layered metal oxide in the X-ray diffraction spectrum is greater than or equal to 0.7, optionally greater than or equal to 0.75, more optionally greater than or equal to 0.8, and It is more optionally greater than or equal to 0.85, and even more optionally greater than or equal to 0.9, but not higher than 1.5, not higher than 1.4, not higher than 1.3, not higher than 1.25, not higher than 1.2.
  • the O3 phase layered metal oxide is in the space group In the hexagonal crystal system, the ratio of the unit cell parameter c to the unit cell parameter a is ⁇ 5, optional ⁇ 5.5.
  • the c/a ratio of the O3 phase layered metal oxide is greater than or equal to 5.6, or greater than or equal to 5.7, or greater than or equal to 5.8, or greater than or equal to 5.9, or greater than or equal to 6.0, or greater than or equal to 6.1 , Or greater than or equal to 6.2, or greater than or equal to 6.3, or greater than or equal to 6.4, or greater than or equal to 6.5, or greater than or equal to 6.6, or greater than or equal to 6.7, or greater than or equal to 6.8, or greater than or equal to 6.9, or Greater than or equal to 7.0, but not higher than 9.0, not higher than 8.5 or not higher than 8.0.
  • the O3 phase layered metal oxide has I(003)/I(104) ⁇ 0.62 in the X-ray diffraction spectrum, optionally between 0.67 and 1.5, and the O3 phase layer Metal oxides are in the space group In the hexagonal crystal system, the ratio of the unit cell parameter c to the unit cell parameter a is ⁇ 5, optional ⁇ 5.5.
  • This O3 phase layered metal oxide has particularly excellent structural stability, and thus exhibits particularly excellent electrical and dynamic properties when applied under high voltage.
  • the primary particles of the O3 phase layered metal oxide have a plate-like structure.
  • the grain size of the primary particles is between 0.05 ⁇ m and 15 ⁇ m, optionally between 0.1 ⁇ m and 5 ⁇ m, such as 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, and 0.5 ⁇ m.
  • the compacted density of the positive electrode active material for a sodium ion battery under a pressure of 8 tons is between 1.5 g/cm 3 and 4.5 g/cm 3 , and optionally 2.5 g/cm 3. Between g/cm 3 and 4g/cm 3.
  • the positive electrode active material is obtained as follows:
  • Ni source and the Mn source are co-precipitated by a co-precipitation method to obtain a nickel manganese metal salt precursor
  • step ii) Solid-phase sintering the nickel-manganese metal salt precursor obtained in step i) with the Na source, Fe source, and M metal source to obtain a positive electrode active material containing O3 phase layered metal oxide.
  • the inventor of the present application found that during the preparation process of the positive electrode active material, the sintering temperature and sintering time will affect the electrical performance and cycle performance of the positive electrode active material.
  • the sintering temperature has a great influence on the performance of the material. This is mainly because when the sintering temperature is lower than the optimal sintering temperature, the reaction is not complete and it is easy to form amorphous materials. The crystallization performance of the material is not good, and it contains impurity phases. The electrochemical performance has a greater impact.
  • the sintering temperature increases, the diffusion coefficient of the material increases, which promotes the diffusion of ions and vacancies, particle rearrangement and other material transfer processes, which is conducive to obtaining products with high crystallinity. Therefore, appropriately increasing the calcination temperature is effective for the reaction. advantageous. However, if the temperature is too high, it is easy to generate hypoxic compounds and promote secondary recrystallization.
  • the sintering is at a temperature of 850-920°C, optionally at a temperature of 890-910°C, more optionally at a temperature of 895-905°C, and most optionally at 900°C. Temperature.
  • the sintering time will also affect the electrochemical properties of the material. As the sintering time increases, ions and vacancies have enough time to carry out the material transfer processes such as diffusion and particle rearrangement, which is conducive to obtaining a product with a more stable structure. Therefore, it is advantageous to extend the sintering time appropriately for the reaction. But too long sintering time is economically disadvantageous and will not significantly improve the structural stability of the product. Therefore, in some embodiments of the present application, sintering is performed for 15-25 hours, optionally for 17-22 hours, more optionally for 19-21 hours, and most optionally for 20 hours.
  • any Ni source, Mn source, Na source, Fe source, or source known to those skilled in the art that are suitable for preparing the cathode active material for the secondary battery can be used.
  • M metal source In the embodiments of the present application, one or more of sulfates, carbonates, metal oxides, phosphates, nitrates, metal hydroxides, or metal halides may be used as raw materials.
  • a complexing agent may be used.
  • the complexing agent is one or more mixed solutions of ammonia, ammonium bicarbonate, ammonium sulfate, ammonium carbonate, citric acid and disodium ethylenediaminetetradioate.
  • a precipitating agent may be used.
  • the precipitating agent is a mixed solution of one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the cathode active material containing the O3 phase layered metal oxide according to the present application has excellent structural stability and is suitable for the high voltage section.
  • FIG. 4 is a perspective view of an embodiment of the sodium ion battery 5.
  • Fig. 5 is an exploded view of Fig. 4. 4 to 5, the sodium ion battery 5 includes a case 51, an electrode assembly 52, a top cover assembly 53, and an electrolyte (not shown).
  • the electrode assembly 52 is housed in the housing 51.
  • the number of electrode assemblies 52 is not limited, and may be one or more.
  • the electrode assembly 52 includes a positive pole piece, a negative pole piece, and a separator. The separator separates the positive pole piece and the negative pole piece.
  • the electrolyte is injected into the casing 51 and impregnates the electrode assembly 52, which includes, for example, a first pole piece, a second pole piece, and an isolation membrane.
  • the sodium ion battery 5 shown in FIG. 4 is a can type battery, but is not limited to this.
  • the sodium ion battery 5 may be a pouch type battery, that is, the casing 51 is replaced by a metal plastic film and the top cover assembly 53 is eliminated.
  • the second aspect of the present application provides a sodium ion battery, which includes a positive pole piece, a negative pole piece, a separator separated between the positive pole piece and the negative pole piece, and an electrolyte.
  • the positive pole piece includes a positive electrode current collector.
  • a positive electrode active material layer provided on at least one side of the positive electrode current collector, wherein the positive electrode active material is a positive electrode active material according to the present application, and the battery has a charge cut-off voltage of 4.2V or higher.
  • the sodium ion battery has a first discharge specific capacity of 120 mAh/g at a voltage of 2.0-4.2V and a capacity retention rate of 87% or higher after 100 cycles at 1C.
  • the third aspect of the present application provides a sodium ion battery, which includes a positive pole piece, a negative pole piece, a separator separated between the positive pole piece and the negative pole piece, and an electrolyte.
  • the positive pole piece includes a positive electrode current collector and The positive electrode active material layer provided on at least one side of the positive electrode current collector, wherein the positive electrode active material is the positive electrode active material according to the present application, and the battery has a charge cut-off voltage of 4.5V or higher.
  • the sodium ion battery has a first discharge specific capacity of 150 mAh/g at a voltage of 2.0-4.5V and a capacity retention rate of 80% or higher after 100 cycles at 1C.
  • the positive electrode sheet containing the positive electrode active material has a certain compaction density.
  • the compaction density TD of the positive pole piece is 1.5 ⁇ TD ⁇ 4.0, optionally 2.0 ⁇ TD ⁇ 4.0.
  • the compaction density of the pole piece is too low, it is not conducive to increasing the volume energy density of the pole piece, and when the compaction density is too high, it is not conducive to the full contact of the electrolyte of the material and the electrochemical performance of the material.
  • the ratio of the average particle size of the positive and negative electrode materials is 0.2 ⁇ A/B ⁇ 3; the optional range is 0.5 ⁇ A/B ⁇ 1, Where A is the average particle size of the positive electrode material, and B is the average particle size of the negative electrode material.
  • A is the average particle size of the positive electrode material
  • B is the average particle size of the negative electrode material.
  • the average particle size of the electrode material should not be too small. If it is too small, it will easily cause problems in the preparation process of the slurry and the pole piece.
  • the A/B is controlled within an appropriate range, and the battery can achieve superior charging and discharging performance at a high rate.
  • A/B is greater than the given range, there may be a phenomenon that the particle size of the negative electrode material is too small or the particle size of the positive electrode material is too large. If the particle size of the negative electrode material is too small, the first-lap coulombic efficiency of the sodium ion battery may be too large. Low; if the particle size of the cathode material is too large, the rate performance of the sodium ion battery is very poor.
  • A/B is less than the given range, the average particle size of the negative electrode material may be too large or the average particle size of the positive electrode material is too small.
  • the average particle size of the negative electrode material is too large, sodium ions will be inserted into the negative electrode material. It cannot be completely embedded, which may lead to the phenomenon of sodium evolution; if the average particle size of the positive electrode material is too small, there will also be problems with the preparation process of the slurry and the pole piece.
  • the present application does not have special restrictions on the preparation method of the sodium ion battery, and the technical solution for preparing the positive electrode active material into a sodium ion battery well known to those skilled in the art may be adopted.
  • FIG. 6 is a perspective view of an embodiment of the battery module 4.
  • the battery module 4 provided by the third aspect of the present application includes the sodium ion battery 5 of the second aspect of the present application.
  • the battery module 4 includes a plurality of sodium ion batteries 5.
  • a plurality of sodium ion batteries 5 are arranged in the longitudinal direction.
  • the battery module 4 can be used as a power source or an energy storage device.
  • the number of sodium ion batteries 5 in the battery module 4 can be adjusted according to the application and capacity of the battery module 4.
  • FIG. 7 is a perspective view of an embodiment of the battery pack 1.
  • Fig. 8 is an exploded view of Fig. 7.
  • the battery pack 1 provided by the fourth aspect of the present application includes the battery module 4 of the third aspect of the present application.
  • the battery pack 1 includes an upper case 2, a lower case 3 and a battery module 4.
  • the upper case 2 and the lower case 3 are assembled together to form a space for accommodating the battery module 4.
  • the battery module 4 is placed in the space of the upper case 2 and the lower case 3 assembled together.
  • the output pole of the battery module 4 passes through one or between the upper case 2 and the lower case 3 to supply power to the outside or charge from the outside.
  • the number and arrangement of the battery modules 4 used in the battery pack 1 can be determined according to actual needs.
  • Fig. 9 is a schematic diagram of an embodiment of a device using a sodium ion battery as a power source.
  • the device provided by the fifth aspect of the present application includes the sodium ion battery 5 of the second aspect of the present application, and the sodium ion battery 5 can be used as a power source for the device.
  • the device using the sodium ion battery 5 is an electric vehicle.
  • the device using the sodium ion battery 5 can be any electric vehicle other than electric vehicles (such as 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 fifth aspect of the present application may include the battery module 4 of the third aspect of the present application.
  • the device provided in the fifth aspect of the present application may also include the battery pack of the fourth aspect of the present application. 1.
  • the button battery is prepared as follows:
  • the positive electrode active material according to the present application, the conductive carbon, and the binder polyvinylidene fluoride (PVDF) are fully stirred and mixed in an appropriate amount of N-methylpyrrolidone (abbreviated as NMP) solvent at a weight ratio of 80:15:5, To form a uniform positive electrode slurry; this slurry is coated on the positive electrode current collector carbon-coated Al foil, and after drying, it is punched into a small disc with a diameter of 14 mm.
  • NMP N-methylpyrrolidone
  • Negative pole piece Use metallic sodium piece.
  • Isolation film There is no special choice, glass fiber or non-woven fabric can be used.
  • the positive electrode sheet, the separator film, and the negative electrode sheet are stacked in sequence, so that the separator film is located between the positive electrode sheet and the negative electrode sheet for isolation, and the prepared electrolyte is injected into the cell to complete the preparation of the button cell.
  • the powder sample X-ray diffractometer (XRD, Bruker D8) obtains powder diffraction data; the X-ray source is CuK ⁇ , the working voltage is 40kV, and the current is 40mA.
  • the sample scan angle range is 10-80 degrees, and the step size is selected as 0.02 degrees.
  • Use VESTA to construct the basic structure of the synthesized material, and then use GENERAL STRUCTURE ANALYSIS SYSTEM software (GSAS) to refine the XRD spectrum, and adjust the atomic parameters in the structure by the least square method, the peak shape parameters used for fitting, and the instrument parameters, etc. , So that the full-spectrum weighted residual variance factor Rwp is minimized.
  • the structure data is exported and used for VESTA analysis and drawing.
  • An X-ray diffractometer was used to determine the grain size of the positive electrode active material.
  • Step 1) Weigh the quality of the positive electrode film with a standard balance, and measure the coating area of the positive electrode film with a ruler, and then calculate the mass per unit area (g/cm 2 ) of the positive electrode film.
  • Step 2): According to the positive electrode film laminate density D ( calculated in g/cm 3 ) the weight per unit area of the positive electrode film (g/cm 2 )/the thickness of the positive electrode film (cm), the positive electrode film laminate is calculated The actual density D, where the thickness of the positive electrode film can be measured by a ten-meter ruler.
  • the sodium ion battery is first charged with a constant current of 1C to a voltage of 4.2V, and then discharged with a constant current of 1C to a voltage of 2.0V. This is a charge-discharge cycle process. The discharge capacity this time is the first cycle. Discharge capacity.
  • the sodium ion battery was subjected to 100 cycles of charge/discharge test according to the above method, and the discharge capacity of the 100th cycle was detected.
  • Capacity retention rate (%) after 100 cycles of sodium ion battery (discharge capacity of sodium ion battery for 100 cycles/discharge capacity of sodium ion battery for first cycle) ⁇ 100%.
  • the sodium ion battery is first charged with a constant current of 1C to a voltage of 4.5V, and then discharged with a constant current of 1C to a voltage of 2.0V. This is a charge-discharge cycle process, and the discharge capacity this time is the first The discharge capacity of the second cycle.
  • the sodium ion battery was subjected to 100 cycles of charge/discharge test according to the above method, and the discharge capacity of the 100th cycle was detected.
  • the capacity retention rate after 100 cycles of the sodium ion battery (%) (discharge capacity of the sodium ion battery after 100 cycles/discharge capacity of the first cycle of the sodium ion battery) ⁇ 100%.
  • NiSO 4 ⁇ 6H2O and MnSO 4 ⁇ H2O are used as Ni source and Mn source, ammonia water is used as complexing agent, NaOH is used as precipitating agent, and nickel manganese hydroxide precursor is prepared by co-precipitation method.
  • Na 2 CO 3 , Fe 3 O 4 , salt or oxide containing doping element M, and nickel manganese hydroxide precursor were fully ground and placed in a tube furnace at a specific temperature After sintering for a period of time, a positive electrode material containing O3 phase layered metal oxide Na a M b Ni c Fe d Mn e O 2 ⁇ shown in Table 1 was obtained.
  • Comparative Examples 1-4 As a control, the positive electrode active materials of Comparative Examples 1-4 were prepared by the above-mentioned method, and the only difference is that Comparative Examples 1-3 did not contain the salt or oxide of the doping element M, and Comparative Example 4 Mg-doped oxides .
  • the positive electrode active material of the present application and the positive electrode active material for comparison, conductive carbon, and binder polyvinylidene fluoride (PVDF) are mixed in an appropriate amount of N-methylpyrrolidone (abbreviated as NMP) solvent at a weight ratio of 80:15:5 Stir and mix thoroughly to form a uniform positive electrode slurry; coat the slurry on the positive electrode current collector carbon-coated Al foil, dry and punch into a small disc with a diameter of 14 mm.
  • NMP N-methylpyrrolidone
  • Negative pole piece Use metallic sodium piece.
  • Isolation film use glass fiber.
  • the positive electrode sheet, the separator film, and the negative electrode sheet are stacked in order, so that the separator film is located between the positive electrode sheet and the negative electrode sheet for isolation, and the prepared electrolyte is injected into the cell to complete the preparation of the button cell.
  • the doping elements in the positive electrode active material in the form of the O3 phase layered metal oxide have a significant impact on the structure and properties of the positive electrode active material, such as the crystallization and the degree of mixing of sodium cations; in addition, The sintering temperature and time of the positive electrode active material will also have an impact on the structural performance, and further affect the electrochemical performance of the sodium ion battery, especially the high-voltage discharge specific capacity and high-voltage cycle performance.
  • the sintering temperature and sintering time will also affect the structural properties of the positive electrode active material (including the crystallization of the positive electrode active material and the degree of mixing of sodium cations) and electrical properties (the high-voltage discharge specific capacity and high-voltage cycle performance of the sodium ion battery). influences. Sintering at 900°C for 20 hours can obtain the best positive electrode active material.

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Abstract

本申请涉及钠离子电池用正极活性材料、由该活性材料制成的钠离子电池、电池模块、电池包及装置。具体地，钠离子电池用正极活性材料，其主要包含O3相层状金属氧化物，O3相层状金属氧化物具有如下分子式：Na aM bNi cFe dMn eO 2±δ(式I)式I中，M为不同于Ni、Fe和Mn的金属阳离子；0.67＜a＜1.1；0＜b＜0.25，可选0.05＜b＜0.15；0＜c＜0.3，可选0.05＜c＜0.25；0＜b+c＜0.55；0.45＜d+e＜1；且b+c+d+e＝1；0≤δ≤0.1，其中，金属阳离子选自Li +、Cu 2+、Zn 2+、Co 2+、Ti 4+中的至少一种。

Description

钠离子电池用正极活性材料、由该活性材料制成的钠离子电池、电池模块、电池包及装置
相关申请的交叉引用
本申请要求享有于2019年09月27日提交的名称为“钠离子电池用正极活性材料、由该活性材料制成的钠离子电池、电池模块、电池包及装置”的中国专利申请201910922651.9的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本申请属于电化学领域，涉及一种钠离子电池用正极活性材料，具体涉及耐高电压的钠离子电池用正极活性材料。本申请还涉及由上述正极活性材料制成的钠离子电池、电池模块、电池包及装置。
背景技术
自从二十世纪七十年代以来，科研工作者们就已经开始关注钠离子可充电电池技术，然而由于锂离子电池的成功商业化，钠离子电池的研发在很长一段时期内都处于停顿的状态。自从2010年以来，锂离子电池技术面临来自高能量密度需求、成本、性能和安全各方面的挑战，钠离子可充电电池技术再次成为电池领域研究的焦点。目前，对于钠离子电池技术，从正负极材料、电解液、隔离膜的开发，到新型化学/电化学体系的设计等都得到了爆发式的发展。
与锂离子电池相似，制约钠离子电池性能的关键因素是其正极材料。在被广泛研究的各种正极材料诸如氧化物、氟化物、硫化物、磷酸盐、焦磷酸盐、金属有机框架/金属六氰化物以及有机化合物中，具有层状结构的过渡金属氧化物正极材料由于具有较高的理论容量、较高的密度、较低的成本以及材料制备的简易性而得到了广泛的关注，成为一种极具潜力的钠离子电池正极材料。
发明内容
本申请的第一方面提供了一种钠离子电池用正极活性材料，其主要包含O3相层状金属氧化物，所述O3相层状金属氧化物具有如下分子式：
Na aM bNi cFe dMn eO 2±δ (式I)
式I中，
M为不同于Ni、Fe、Mn的金属阳离子；0.67＜a＜1.1；0＜b＜0.25，可选0.05＜b＜0.15；0＜c＜0.3，可选0.05＜c＜0.25；0＜b+c＜0.55；0.45＜d+e＜1；且b+c+d+e＝1；0≤δ≤0.1，
其中，所述金属阳离子选自Li +、Cu 2+、Zn 2+、Co 2+、Ti 4+中的至少一种。
在根据本申请的钠离子电池用正极活性材料中，掺杂有特定金属阳离子的O3相层状金属氧化物具有较高的结构稳定性，当在高电压下应用时不仅可以保持较好的循环性能，还能够稳定地发挥电性能。发明人惊讶地发现，当在O3相层状金属氧化物中掺杂Li +、Cu 2+、Zn 2+、Co 2+、Ti 4+中的至少一种时可以得到具有较高的I 003/I 104的比值O3相层状金属氧化物，该材料的结构有序性更好，金属-氧(MO)键的结合更牢固。另外/或者，上述O3层状金属氧化物具有较好的结晶结构，其是空间群为
Figure PCTCN2020113822-appb-000001
的六方晶系，其晶胞参数c与晶胞参数a的比值较大，该材料的结晶性能优异， 具有最佳的层状结构。具有这样结构的金属氧化物，当在较高电压下使用时，可以实现较好的循环性能，同时又能稳定地发挥其电性能。
在根据上述第一方面所述的钠离子电池用正极活性材料中，所述O3相层状金属氧化物在X射线衍射谱中的I(003)/I(104)≥0.62，可选介于0.67和1.5之间，其中I(003)表示O3相层状金属氧化物的(003)晶面峰强度，I(104)表示O3相层状金属氧化物的(104)晶面峰强度，I(003)/I(104)反映了所述O3相层状金属氧化物中钠金属阳离子的混排度。由此，O3相层状金属氧化物的过渡金属和氧(TM-O)的相互作用力得到了增强。
在根据上述第一方面所述的任意钠离子电池用正极活性材料中，所述O3相层状金属氧化物是空间群为
Figure PCTCN2020113822-appb-000002
的六方晶系，其中晶胞参数c与晶胞参数a的比值≥5，可选≥5.5。由此，O3相层状金属氧化物的结晶性能得到了增强。
在根据上述第一方面所述的任意钠离子电池用正极活性材料中，所述O3相层状金属氧化物在X射线衍射谱中的I(003)/I(104)≥0.62，可选介于0.67和1.5之间，并且所述O3相层状金属氧化物是空间群为
Figure PCTCN2020113822-appb-000003
的六方晶系，其中晶胞参数c与晶胞参数a的比值≥5，可选≥5.5。由此，这样的O3相层状金属氧化物具有特别优异的结构稳定性，因而当在高电压下应用时显示特别优异的电性能和动力学性能。
在根据上述第一方面所述的任意钠离子电池用正极活性材料中，所述O3相层状金属氧化物的一次颗粒为片状结构。由此，得到的正极活性材料具有理想的结构稳定性和电性能。
在根据上述第一方面所述的任意钠离子电池用正极活性材料中，所述一次颗粒的晶粒粒径介于0.05微米和15微米之间，可选介于0.1微米和5微米之间。由此，得到的正极活性材料具有理想的结构稳定性和电性能。
在根据上述第一方面所述的任意钠离子电池用正极活性材料中，所述正极活性材料在8吨压力下的压实密度介于1.5g/cm 3和4.5g/cm 3之间，可选地介于2.5g/cm 3和4g/cm 3之间。由此，得到的正极活性材料具有理想的结构稳定性和电性能。
在根据上述第一方面所述的任意钠离子电池用正极活性材料中，所述正极活性材料是通过如下获得的：i)在络合剂和沉淀剂的存在下，通过共沉淀方法，使Ni源和Mn源进行共沉淀，从而得到镍锰金属盐前驱体，以及ii)将步骤i)得到的镍锰金属盐前驱体与Na源、Fe源、M金属源进行固相烧结，从而得到包含O3相层状金属氧化物的正极活性材料。可选地，所述烧结在850-920℃的温度下进行15-25小时。由此，得到电性能和循环性能优异的正极活性材料。
在根据上述第一方面所述的任意钠离子电池用正极活性材料中，所述烧结在850-920℃的温度下、可选在890-910℃的温度下、更可选在895-905℃的温度下、最可选在900℃的温度下进行。由此，得到具有适宜的结晶性能的正极活性材料。
在根据上述第一方面所述的任意钠离子电池用正极活性材料中，所述烧结进行15-25小时，可选进行17-22小时，更可选进行19-21小时，最可选进行20小时。由此，得到具有优异电化学性能的正极活性材料。
本申请的第二方面提供了钠离子电池，其包括正极极片、负极极片、间隔于所述正极极片和负极极片之间的隔离膜和电解液，所述正极极片包含包括正极集流体以及设置于所述正极集流体至少一侧的正极活性材料层，其中所述正极活性材料为根据本申请的正极活性材料，并且所述电池具有4.2V或更高的充电截止电压。
在根据本申请第二方面所述的钠离子电池中，所述电池在2.0-4.2V的电压下具有120mAh/g的首次放电比容量且在1C下100圈后具有87％ 或更高的容量保持率。
本申请的第三方面提供了钠离子电池，包括正极极片、负极极片、间隔于所述正极极片和负极极片之间的隔离膜和电解液，所述正极极片包含包括正极集流体以及设置于所述正极集流体至少一侧的正极活性材料层，其中所述正极活性材料为根据本申请的正极活性材料，并且所述电池具有4.5V或更高的充电截止电压。
在根据本申请第三方面所述的钠离子电池中，所述电池在2.0-4.5V的电压下具有150mAh/g的首次放电比容量且在1C下100圈后具有80％或更高的容量保持率。
本申请的第四方面提供了一种电池模块，其包括本申请的第二方面或第三方面所述的钠离子电池。
本申请的第五方面提供了一种电池包，其包括本申请的第四方面所述的电池模块。
本申请的第六方面提供了一种装置，其包括本申请的第二方面或第三方面所述的钠离子电池，所述钠离子电池用作所述装置的电源或能量存储单元；可选地，所述装置包括电动车辆、混合动力电动车辆、插电式混合动力电动车辆、电动自行车、电动踏板车、电动高尔夫球车、电动卡车、电动船舶、储能系统。
本申请的电池模块、电池包和装置包括本申请提供的钠离子电池，因而至少具有与所述钠离子电池相同的优势。
本申请的一个或多个实施方案的细节在以下的说明书中阐明。根据说明书和权利要求，本申请其它特征、目的和优点将变得清楚。
定义
描述本申请的内容时，不使用数量词时(尤其在权利要求书的内容中)应解释为涵盖单数和复数，除非另有说明或者与上下文明显矛盾。
在方法被描述为包括或包含特定工艺步骤的情况下，预计该方法中并不排除未被明确指明的可选工艺步骤，并且该方法也可由所涉及的工艺步骤构成或组成。
为了简便，本文仅明确地公开了一些数值范围。然而，任意下限可以与任何上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，尽管未明确记载，但是范围端点间的每个点或单个数值都包含在该范围内。因而，每个点或单个数值可以作为自身的下限或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
在涉及O3相层状金属氧化物的上下文中，I(003)/I(104)被用于反映钠金属阳离子在O3相层状金属氧化物中的混排度，其中I(003)表示正极活性材料在(003)晶面的峰强度，I(104)表示在(104)晶面的峰强度。通常I(003)/I(104)的比值越大，钠金属阳离子在O3相层状金属氧化物的混排度越低，意味着O3相层状金属氧化物的结构有序性越高，结构越稳定。
在涉及O3相层状金属氧化物的上下文中，“晶胞参数c与晶胞参数a的比值”用于表征O3相层状金属氧化物的结晶结构。通常，c/a比值大于5时，材料中被认为结晶良好，存在层状结构。该比值越大，说明层状结构在材料中所占比例越高，所形成的层状结构越好。
在涉及O3相层状金属氧化物的上下文中，“六方晶系”是指具有如下晶胞参数的晶系结构，其中晶胞参数a＝b≠c，且α＝β＝90°，γ＝120°。
在涉及O3相层状金属氧化物的上下文中，“一次颗粒”是指该O3相层状金属氧化物的结晶颗粒，其不同于结晶颗粒团聚后形成的颗粒(二次颗粒)。
术语“可选的”和“可选地”是指在某些情况下可提供某些益处的本申请实施方案。然而，在相同或其他情况下，其他实施方案也可能是可选的。另外，一个或多个可选的实施方案的叙述不意味着其他实施方案是不可用的，并且不旨在将其他实施方案排除在本申请范围外。
附图说明
图1为采用本申请的实施例5的钠离子电池用正极活性材料的X射线衍生谱。
图2为采用本申请的实施例5的钠离子电池用正极活性材料制成的扣式电池在不同电压下的首次充放电曲线。
图3为采用本申请的实施例5的钠离子电池用正极活性材料制成的扣式电池在不同电压下的循环性能。
图4是钠离子电池的一实施方式的立体图。
图5是图4的分解图。
图6是电池模块的一实施方式的立体图。
图7是电池包的一实施方式的立体图。
图8是图7的分解图。
图9是钠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钠离子电池
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，所描述的实施例仅仅是本申请的一部分，并非全部。基于本申请的实施例，本领域普通技术人员对本申请进行的常规修改或变形而获得的所有技术方案，均落在本申请的保护范围之内。
第一方面，本申请提供了一种钠离子电池用正极活性材料，其主要包含O3相层状金属氧化物，O3相层状金属氧化物具有如下分子式：
Na aM bNi cFe dMn eO 2±δ (式I)
式I中，M为不同于Ni、Fe和Mn的金属阳离子；0.67＜a＜1.1；0＜b＜0.25，可选0.05＜b＜0.15；0＜c＜0.3，可选0.05＜c＜0.25；0＜b+c＜0.55；0.45＜d+e＜1；且b+c+d+e＝1；0≤δ≤0.1，其中，金属阳离子选自Li +、Cu 2+、Zn 2+、Co 2+、Ti 4+中的至少一种。
在钠离子电池的生产过程中，主要采用具有层状结构的氧化物作为正极活性材料。根据层状结构氧化物稳定相结构，可将其分类为P2相和O3相层状金属氧化物，其中O3相NaxMO 2(0.67＜X≤1；M＝Fe、Mn、Ni等中的一种以上金属)在比容量和比能量两方面都具有极大的优势，被认为是极具潜力的钠离子电池正极材料。但目前并没有寻找到在可接受的成本下仍具有高比容量且寿命长的适合商业化的O3相层状过渡金属氧化物正极材料，这主要是因为O3相层状过渡金属氧化物正极材料在相关电解液 体系中存在着在高电压区段(＞4.1V)易发生不可逆相转变的问题。这种弱耐高压性使得材料在高电压区段充放电过程中易发生结构畸变，导致材料的长期循环稳定性较差。为了提高包含O3相层状过渡金属氧化物的正极材料的循环性能，不得不降低材料的充放电电压以牺牲正极材料的比容量为代价，这也就降低了该类材料的商业化价值。迄今为止，电池工业中还没有一种适用于高电压钠离子电池且能够兼顾电池的比容量和循环稳定性二者的O3相层状金属氧化物正极活性材料。
在根据本申请的实施方式中，钠离子电池用正极活性材料主要包含O3相层状金属氧化物。换句话说，O3相层状金属氧化物占正极活性材料的主要部分。在本申请的一个实施方式中，钠离子电池用正极活性材料包含相对于正极活性材料的总重量90wt％或更高的O3相层状金属氧化物，可选95wt％或更高的O3相层状金属氧化物，更可选98wt％或更高的O3相层状金属氧化物，还要更可选99wt％或更高的O3相层状金属氧化物。最可选地，钠离子电池用正极活性材料由O3相层状金属氧化物组成。
本申请的发明人惊讶地发现，在根据本申请的钠离子电池用正极活性材料中，掺杂有特定金属阳离子的O3相层状金属氧化物具有较高的结构稳定性，当在高电压下应用时不仅能够稳定地发挥其电性能，还得到明显改善的循环性能。并未受缚与任何理论，申请人推测原因在于，特定种类的金属元素掺杂改性O3相钠镍锰铁氧化物后，能够有效地抑制该材料在高电压区段(例如＞4.1V)的不可逆相转变(P3-P3’)，保证了材料在充放电过程中的结构稳定性，从而达到了容量和循环性能的较佳平衡。在高电压区段的不可逆相转变(P3-P3’)主要是Ni 3+的J-T效应引起的。在根据本申请的O3相层状金属氧化物中，掺杂的金属增强了过渡金属和氧(TM-O)的相互作用力，特别是镍和氧(Ni-O)的作用力，能有效的抑制Ni 3+的J-T效应，从而达到抑制高电压区不可逆相转变的目的。
在本申请的实施方式中，适于掺杂O3相层状金属氧化物的金属阳离子选自Li +、Cu 2+、Zn 2+、Co 2+、Ti 4+中的至少一种。特别适于掺杂O3相层状金属氧化物的金属阳离子是Li +。这些特定种类的金属阳离子的掺杂对于提高金属氧化物的结构稳定性是至关重要的。本申请的发明人惊讶地发现，由这些特定种类的金属阳离子掺杂的O3相层状金属氧化物，较之相关技术公开的用其它金属阳离子(例如Mg 2+)掺杂O3相层状金属氧化物，具有提高的结构稳定性，结果根据本申请得到的O3相层状金属氧化物当在高电压下应用时显示明显更优的电性能和动力学性能。
采用以上特定种类的金属阳离子进行掺杂增强了O3相层状金属氧化物中过渡金属和氧(TM-O)的相互作用力，这体现在I(003)/I(104)参数上。在本申请的一些实施方式中，O3相层状金属氧化物在X射线衍射谱中的I(003)/I(104)≥0.62，其中I(003)表示O3相层状金属氧化物的(003)晶面峰强度，I(104)表示O3相层状金属氧化物的(104)晶面峰强度，I(003)/I(104)反映了O3相层状金属氧化物中钠金属阳离子的混排度。可选地，O3相层状金属氧化物在X射线衍射谱中的I(003)/I(104)大于或等于0.7，可选地大于或等于0.75，更可选地大于或等于0.8，还要更可选地大于或等于0.85，甚至还要更可选地大于或等于0.9，但不高于1.5，不高于1.4，不高于1.3，不高于1.25，不高于1.2。
而且，采用以上特定种类的金属阳离子进行掺杂还增强了O3相层状金属氧化物的结晶性能，这体现在晶胞参数c与晶胞参数a的比值上。在本申请的一些实施方式中，O3相层状金属氧化物是空间群为
Figure PCTCN2020113822-appb-000004
的六方晶系，其中晶胞参数c与晶胞参数a的比值≥5，可选≥5.5。可选地，O3相层状金属氧化物的c/a比大于或等于5.6，或大于或等于5.7，或大于或等于5.8，或大于或等于5.9，或大于或等于6.0，或大于或等于6.1，或大于或等于6.2，或大于或等于6.3，或大于或等于6.4，或大于或等于6.5，或 大于或等于6.6，或大于或等于6.7，或大于或等于6.8，或大于或等于6.9，或大于等于7.0，但不高于9.0，不高于8.5或不高于8.0。
在本申请的一些可选实施方式中，O3相层状金属氧化物在X射线衍射谱中的I(003)/I(104)≥0.62，可选在0.67和1.5之间，并且O3相层状金属氧化物是空间群为
Figure PCTCN2020113822-appb-000005
的六方晶系，其中晶胞参数c与晶胞参数a的比值≥5，可选≥5.5。这种O3相层状金属氧化物具有特别优异的结构稳定性，因而当在高电压下应用时显示特别优异的电性能和动力学性能。
可选地，根据本申请的一些实施方式，O3相层状金属氧化物的一次颗粒为片状结构。在本申请的一些实施方式中，一次颗粒的晶粒粒径介于0.05微米和15微米之间，可选介于0.1微米和5微米之间，例如为0.2微米、0.3微米、0.4微米、0.5微米、0.6微米、0.7微米、0.8微米、0.9微米、1微米、1.5微米、2微米、2.5微米、3微米、3.5微米、4微米、4.5微米或4.8微米。
可选地，根据本申请的一些实施方式，钠离子电池用正极活性材料在8吨压力下的压实密度介于1.5g/cm 3和4.5g/cm 3之间，可选地介于2.5g/cm 3和4g/cm 3之间。
在本申请的一些实施方式中，正极活性材料是通过如下获得的：
i)在络合剂和沉淀剂的存在下，通过共沉淀方法，使Ni源和Mn源进行共沉淀，从而得到镍锰金属盐前驱体，以及
ii)将步骤i)得到的镍锰金属盐前驱体与Na源、Fe源、M金属源进行固相烧结，从而得到包含O3相层状金属氧化物的正极活性材料。
本申请的发明人发现，在正极活性材料的制备过程中，烧结温度和烧结时间会影响正极活性材料的电性能和循环性能。
烧结温度对材料的性能影响较大，这主要是因为当烧结温度低于最佳烧结温度时，反应不完全，容易生成无定形材料，材料的结晶性能不 好，且含有杂相，对材料的电化学性能影响较大。但随着烧结温度的升高，物料的扩散系数增大，促进了离子和空位的扩散、颗粒重排等物质传递过程，从而有利于得到结晶度高的产物，因此适当提高煅烧温度对反应是有利的。但是温度过高，容易生成缺氧型化合物而且还会促进二次再结晶，同时材料的晶粒变大，比表面积变小，不利于钠离子在材料中的脱出和嵌入。因此，在本申请的一些实施方式中，烧结在850-920℃的温度下、可选在890-910℃的温度下、更可选在895-905℃的温度下、最可选在900℃的温度下进行。
烧结时间也会对材料的电化学性能产生影响。随着烧结时间的增加，离子和空位有足够的时间进行扩散、颗粒重排等物质传递过程，从而有利于得到结构更为稳定的产物，因此适当延长烧结时间对反应是有利的。但是烧结时间过长从经济上来说是不利的，不会显著提高产物的结构稳定性。因此，在本申请的一些实施方式中，烧结进行15-25小时，可选进行17-22小时，更可选进行19至21小时，最可选进行20小时。
在根据本申请的钠离子电池用正极活性材料的制备过程中，可以使用任何本领域技术人员已知的适用于制备二次电池用正极活性材料的Ni源、Mn源、Na源、Fe源、M金属源。在本申请的实施方式中，可以使用硫酸盐、碳酸盐、金属氧化物、磷酸盐、硝酸盐、金属氢氧化物或金属卤化物中的一种或多种作为原料。
在根据本申请的钠离子电池用正极活性材料的制备过程中，可以使用络合剂。络合剂为氨水、碳酸氢氨、硫酸铵、碳酸铵、柠檬酸和乙二胺四二酸二钠中的一种或一种以上混合溶液。
在根据本申请的钠离子电池用正极活性材料的制备过程中，可以使用沉淀剂。沉淀剂为氢氧化钠、氢氧化钾和氢氧化锂中的一种或一种以上的混合溶液。
如上所述，根据本申请的含有O3相层状金属氧化物的正极活性材料具有优异的结构稳定性，适用于高电压区段。
其次说明根据本申请第二方面的钠离子电池。
图4是钠离子电池5的一实施方式的立体图。图5是图4的分解图。参照图4至图5，钠离子电池5包括壳体51、电极组件52、顶盖组件53以及电解液(未示出)。
电极组件52收容于壳体51内。电极组件52的数量不受限制，可以为一个或多个。电极组件52包括正极极片、负极极片、隔离膜。隔离膜将正极极片和负极极片隔开。电解液注入在壳体51内并浸渍电极组件52，电极组件包括例如第一极片、第二极片以及隔离膜。
注意的是图4所示的钠离子电池5为罐型电池，但不限于此，钠离子电池5可以是袋型电池，即壳体51由金属塑膜替代且取消顶盖组件53。
因此，本申请第二方面提供了一种钠离子电池，包括正极极片、负极极片、间隔于正极极片和负极极片之间的隔离膜和电解液，正极极片包含包括正极集流体以及设置于正极集流体至少一侧的正极活性材料层，其中正极活性材料为根据本申请的正极活性材料，并且电池具有4.2V或更高的充电截止电压。该钠离子电池在2.0-4.2V的电压下具有120mAh/g的首次放电比容量且在1C下100圈后具有87％或更高的容量保持率。
本申请的第三方面提供了一种钠离子电池，包括正极极片、负极极片、间隔于正极极片和负极极片之间的隔离膜和电解液，正极极片包含包括正极集流体以及设置于正极集流体至少一侧的正极活性材料层，其中正极活性材料为根据本申请的正极活性材料，并且电池具有4.5V或更高的充电截止电压。该钠离子电池在2.0-4.5V的电压下具有150mAh/g的首次放电比容量且在1C下100圈后具有80％或更高的容量保持率。
在根据本申请的钠离子电池中，包含正极活性材料的正极极片具有一定的压实密度。可选地，正极极片的压实密度TD为1.5≤TD≤4.0，可选2.0≤TD≤4.0。极片压实密度太低时不利于提高极片的体积能量密度，压实密度太高时不利于材料的电解液的充分接触，不利于材料的电化学发挥。
在根据本申请的正极活性材料与硬碳负极材料组成钠离子电池时，正负极材料的平均粒径之比为0.2＜A/B＜3；可选范围为0.5＜A/B＜1，其中A为正极材料的平均粒径，B为负极材料的平均粒径。电极材料平均粒径越小，其电子导电性越好，钠离子电池的倍率性能越好。但是电极材料的平均粒径不宜过小，过小则容易造成浆料以及极片制备工艺问题。在根据本申请的实施方式中，将A/B控制在适当范围内，可以实电池现高倍率下优越的充电和放电性能。当A/B大于所给范围时，可能有负极材料的粒径过小或者正极材料的粒径过大的现象，如果是负极材料的粒径过小，则钠离子电池的首圈库伦效率过低；如果是正极材料的粒径过大，则钠离子电池的倍率性能很差。当A/B小于所给范围时，可能有负极材料的平均粒径过大或者正极材料的平均粒径过小的情况，如果是负极材料的平均粒径过大，则钠离子嵌入负极材料时不能完全嵌入进去，从而可能导致析钠现象；如果是正极材料的平均粒径过小，则同样会有浆料和极片的制备工艺问题。
本申请对钠离子电池的制备方法没有特殊的限制，采用本领域技术人员熟知的将正极活性材料制备成钠离子电池的技术方案即可。
接下来说明本申请第四方面的电池模块。
图6是电池模块4的一实施方式的立体图。
本申请第三方面提供的电池模块4包括本申请的第二方面的钠离子电池5。
参照图6，电池模块4包括多个钠离子电池5。多个钠离子电池5 沿纵向排列。电池模块4可以作为电源或储能装置。电池模块4中的钠离子电池5的数量可以根据电池模块4的应用和容量进行调节。
接下来说明本申请第五方面的电池包。
图7是电池包1的一实施方式的立体图。图8是图7的分解图。
本申请第四方面提供的电池包1包括本申请的第三方面的电池模块4。
具体地，参照图7和图8，电池包1包括上箱体2、下箱体3以及电池模块4。上箱体2和下箱体3组装在一起并形成收容电池模块4的空间。电池模块4置于组装在一起的上箱体2和下箱体3的空间内。电池模块4的输出极从上箱体2和下箱体3的其中之一或二者之间穿出，以向外部供电或从外部充电。电池包1采用的电池模块4的数量和排列可以依据实际需要来确定。
接下来说明本申请第六方面的装置。
图9是钠离子电池作为电源的装置的一实施方式的示意图。
本申请第五方面提供的装置包括本申请的第二方面的钠离子电池5，钠离子电池5可以用作装置的电源。在图9中，采用钠离子电池5的装置为电动汽车。当然不限于此，采用钠离子电池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、电子设备及储能系统。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，本申请第五方面提供的装置可包括本申请的第三方面的电池模块4，当然，本申请第五方面提供的装置也可包括本申请的第四方面的电池包1。
在本申请的一个实施方式中，扣式电池通过如下制备：
1.正极极片的制备：
将根据本申请的正极活性材料与导电炭、粘结剂聚偏二氟乙烯(PVDF)按80∶15∶5重量比在适量的N-甲基吡咯烷酮(简写为NMP)溶剂中充分搅拌混合，使其形成均匀的正极浆料；将此浆料涂覆于正极集流体涂炭Al箔上，干燥后冲成直径为14mm的小圆片。
2、电解液的制备：
将等量体积的碳酸亚乙酯溶解在碳酸亚丙酯中，然后将适量的高氯酸钠盐均匀溶解在混合溶剂中备用。
3、负极极片：选用金属钠片。
4、隔离膜：没有特殊选择，可选用玻璃纤维或者无纺布。
5、扣电池的制备：
将正极片、隔离膜、负极片按顺序叠好，使隔离膜处于正极片和负极片之间起到隔离的作用，将制备好的电解液注入到电芯中，即完成扣电池的制备。
实施例
为了便于理解本申请，本申请列举实施例如下。本技术领域人员应该明了，所述实施例仅仅用于帮助理解本申请，不应该视为本申请的具体限制。
测试方法
X射线衍射以及数据精修
粉末样品X射线衍射仪(XRD，布鲁克D8)获取粉末衍射数据；X射线源选用的是CuKα，工作电压为40kV，电流为40mA。样品扫描角度范围为10-80度，步长选择为0.02度。利用VESTA构建所合成的材料的基本结构，然后采用GENERAL STRUCTURE ANALYSIS SYSTEM软 件(GSAS)对XRD谱图进行精修，通过最小二乘法调节结构中的原子参数、拟合所用峰型参数以及仪器参数等，使得全谱加权剩余差方因子Rwp达到最小。精修达到要求后导出结构数据并用VESTA分析作图。
晶粒尺寸
采用X射线衍射仪测定正极活性材料的晶粒尺寸。
正极膜层的压实密度
步骤1)：分别通过标准天平称量正极膜层质量、通过直尺测量正极膜层涂布面积，然后可计算正极膜层单位面积质量(g/cm 2)。
步骤2)：根据正极膜层压实密度D(以g/cm 3计)＝正极膜层单位面积的质量(g/cm 2)/正极膜层厚度(cm)，计算得出正极膜层压实密度D，其中正极膜层厚度可通过万分尺测量。
钠离子电池在高电压下的首次放电比容量
在2至4.2V下，按照0.1C充电至4.2V，静置2min，此时的充电容量记为C0，然后按照0.1C放电至2V，此时的放电容量为在2-4.2V下的首次放电比容量，记为D0。
同样地，在2至4.5V下，按照0.1C充电至4.5V，静置2min，此时的充电容量记为C0，然后按照0.1C放电至2V，此时的放电容量为在2-4.5V下的首次放电比容量，记为D1。
钠离子电池在高电压下的循环性能
在25℃下，将钠离子电池先以1C恒流充电至电压为4.2V，然后以1C恒流放电至电压为2.0V，此为一个充放电循环过程，此次的放电容量 为首次循环的放电容量。将钠离子电池按照上述方法进行100次循环充电/放电测试，检测得到第100次循环的放电容量。
钠离子电池循环100次后的容量保持率(％)＝(钠离子电池循环100次的放电容量/钠离子电池首次循环的放电容量)×100％。
同样地，在25℃下，将钠离子电池先以1C恒流充电至电压为4.5V，然后以1C恒流放电至电压为2.0V，此为一个充放电循环过程，此次的放电容量为首次循环的放电容量。将钠离子电池按照上述方法进行100次循环充电/放电测试，检测得到第100次循环的放电容量。
钠离子电池循环100次后的容量保持率(％)＝(钠离子电池循环100次的放电容量/钠离子电池首次循环的放电容量)×100％。
正极活性材料的制备
首先以NiSO 4·6H2O和MnSO 4·H2O为Ni源和Mn源，氨水为络合剂，NaOH为沉淀剂，通过共沉淀方法制备得到氢氧化镍锰前驱体。随后，以下表1所示，将Na 2CO 3、Fe 3O 4、含掺杂元素M的盐或氧化物和氢氧化镍锰前驱体充分研磨后放置在管式炉中在特定的温度下烧结一段时间，从而得到表1所示含有O3相层状金属氧化物Na aM bNi cFe dMn eO 2±δ的正极材料。
作为对照，对比例1-4的正极活性材料是采用上述方法制备的，不同之处仅在于对比例1-3未含掺杂元素M的盐或氧化物，对比例4掺杂Mg的氧化物。
根据以上测试部分所示，测定本申请的正极活性材料和对照用正极活性材料的I003/I104的比值和晶胞参数c/a的比值，结果汇总在下表1中。
钠离子电池的制造
1、正极极片的制备：
将本申请的正极活性材料和对照用正极活性材料与导电炭、粘结剂聚偏二氟乙烯(PVDF)按80∶15∶5重量比在适量的N-甲基吡咯烷酮(简写为NMP)溶剂中充分搅拌混合，使其形成均匀的正极浆料；将此浆料涂覆于正极集流体涂炭Al箔上，干燥后冲成直径为14mm的小圆片。
2、电解液的制备：
将等量体积的碳酸亚乙酯溶解在碳酸亚丙酯中，然后将适量的高氯酸钠盐均匀溶解在混合溶剂中形成1mol/L的电解液，备用。
3、负极极片：选用金属钠片。
4、隔离膜：选用玻璃纤维。
5、扣电池的制备：
将正极片、隔离膜、负极片按顺序叠好，使隔离膜处于正极片和负极片之间起到隔离的作用，将制备好的电解液注入到电芯中，即完成扣电池的制备。
根据以上测试部分所示，测定以上制成的扣式电池的首次放电比容量和循环性能，结果汇总在下表1中。
Figure PCTCN2020113822-appb-000006
由以上表1的数据可以看出，O3相层状金属氧化物形式的正极活性材料中的掺杂元素对该正极活性材料的结晶和钠阳离子的混排度等结构性能有显著影响；另外，正极活性材料的烧结温度和时间也会对结构性能有影响，进而进一步影响钠离子电池的电化学性能尤其是高压放电比容量和高压循环性能。
从实施例1-5和对比例1-3在表1中的I(003)/I(104)值的变化可知，掺杂改性后的O3-Na 0.85M bNi 0.175Fe 0.2Mn 0.525O 2相对于未经掺杂的O3-Na 0.9Ni 0.3Mn 0.4Fe 0.3O 2材料具有更优异的结构稳定性，从而表现出优异的综合电化学性能，特别在高电压区段显示出优异的综合电化学性能，因此该材料作为钠离子电池正极材料具有极大的潜在应用价值。
而且，从实施例1-5和对比例4在表1中的I(003)/I(104)值的变化可知，采用特定金属掺杂改性后的O3-Na 0.85M bNi 0.175Fe 0.2Mn 0.525O 2相对于采用Mg金属掺杂的O3-Na 0.9Ni 0.3Mn 0.4Fe 0.3O 2材料具有更优异的结构稳定性，从而表现出优异的综合电化学性能，特别在高电压区段显示出优异的综合电化学性能，这在本申请之前是难以预见的。
另外，烧结温度和烧结时间也会对正极活性材料的结构性能(包括正极活性材料的结晶和钠阳离子的混排度)和电性能(钠离子电池的高压放电比容量和高压循环性能)造成一定影响。在900℃下烧结20小时可以得到性能最优的正极活性材料。
此外，在那些使用类似于“A，B和C等中的至少一个”的约定的情况下，这样的结构通常是在本领域技术人员会理解的约定的意义(例如，“具有A，B和C中至少一个的系统”将包括但不限于单独有A，单独有B，单独由C，有A和B，有A和C，有B和C和/或有A、B和C等的系统)。在那些使用类似于“A、B或C等中的至少一个”的约定的情况下，这样的结构是在本领域技术人员会理解的约定的意义(例如， “具有A、B或C中至少一个的系统”将包括但不限于单独有A，单独有B，单独有C，有A和B，有A和C，有B和C和/或有A、B和C等)。本领域技术人员将进一步理解，实际上，无论是在说明书、权利要求书还是附图中，呈现两个或更多个替代术语的任何析取词和/或短语应被理解为考虑包括这些术语之一、这些术语中的一个或两个的术语的可能性。例如，短语“A或B”将被理解为包括“A”或“B”或“A和B”的可能性。
此外，在根据马库什组描述本公开的特征或方面的情况下，本领域技术人员将认识到，本公开也因此根据马库什组的任何单个成员或成员的子集进行描述。
尽管本申请参照大量实施方式和实施例进行描述，但是本领域普通技术人员根据本申请公开的内容能够认识到可以设计其它实施方式，这并未脱离本申请的保护范围和精神。

Claims (17)

  1. 一种钠离子电池用正极活性材料，其主要包含O3相层状金属氧化物，所述O3相层状金属氧化物具有如下分子式：
    Na aM bNi cFe dMn eO 2±δ  (式I)
    式I中，
    M为不同于Ni、Fe和Mn的金属阳离子；0.67＜a＜1.1；0＜b＜0.25，可选0.05＜b＜0.15；0＜c＜0.3，可选0.05＜c＜0.25；0＜b+c＜0.55；0.45＜d+e＜1；且b+c+d+e＝1；0≤δ≤0.1，
    其中，所述金属阳离子选自Li +、Cu 2+、Zn 2+、Co 2+、Ti 4+中的至少一种。
  2. 如权利要求1所述的钠离子电池用正极活性材料，其中，所述O3相层状金属氧化物在X射线衍射谱中的I(003)/I(104)≥0.62，可选介于0.67和1.5之间，其中I(003)表示O3相层状金属氧化物的(003)晶面峰强度，I(104)表示O3相层状金属氧化物的(104)晶面峰强度，I(003)/I(104)反映了所述O3相层状金属氧化物中钠金属阳离子的混排度。
  3. 如权利要求1或2所述的钠离子电池用正极活性材料，其中，所述O3相层状金属氧化物是空间群为
    Figure PCTCN2020113822-appb-100001
    的六方晶系，其中晶胞参数c与晶胞参数a的比值≥5，可选≥5.5。
  4. 如权利要求1至3中任意一项所述的钠离子电池用正极活性材料，其中，所述O3相层状金属氧化物在X射线衍射谱中的I(003)/I(104)≥0.62，可选介于0.67和1.5之间，并且所述O3相层状金属氧化物是空间群为
    Figure PCTCN2020113822-appb-100002
    的六方晶系，其中晶胞参数c与晶胞参数a的比值≥5，可选≥5.5。
  5. 如权利要求1至4中任意一项所述的钠离子电池用正极活性材料， 其中，所述O3相层状金属氧化物的一次颗粒为片状结构。
  6. 如权利要求5所述的钠离子电池用正极活性材料，其中，所述一次颗粒的晶粒粒径介于0.05微米和15微米之间，可选介于0.1微米和5微米之间。
  7. 如权利要求1至6中任意一项所述的钠离子电池用正极活性材料，其中，所述正极活性材料在8吨压力下的压实密度介于1.5g/cm 3和4.5g/cm 3之间，可选地介于2.5g/cm 3和4g/cm 3之间。
  8. 如权利要求1至7中任意一项所述的钠离子电池用正极活性材料，其中，所述正极活性材料是通过如下获得的：
    i)在络合剂和沉淀剂的存在下，通过共沉淀方法，使Ni源和Mn源进行共沉淀，从而得到镍锰金属盐前驱体，以及
    ii)将步骤i)得到的镍锰金属盐前驱体与Na源、Fe源、M金属源进行固相烧结，从而得到包含O3相层状金属氧化物的正极活性材料。
  9. 如权利要求8所述的钠离子电池用正极活性材料，其中，所述烧结在850-920℃的温度下、优选在890-910℃的温度下、更优选在895-905℃的温度下、最优选在900℃的温度下进行。
  10. 如权利要求8或9所述的钠离子电池用正极活性材料，其中，所述烧结进行15-25小时，优选进行17-22小时，更优选进行19-21小时，最优选进行20小时。
  11. 一种钠离子电池，包括正极极片、负极极片、间隔于所述正极极片和负极极片之间的隔离膜和电解液，所述正极极片包含包括正极集流体以及设置于所述正极集流体至少一侧的正极活性材料层，其中所述正极活性材料为权利要求1至10中任意一项所述的正极活性材料，并且所述电池具有4.2V或更高的充电截止电压。
  12. 如权利要求11所述的钠离子电池，其中，所述电池在2.0-4.2V的 电压下具有120mAh/g的首次放电比容量且在1C下100圈后具有87％或更高的容量保持率。
  13. 一种钠离子电池，包括正极极片、负极极片、间隔于所述正极极片和负极极片之间的隔离膜和电解液，所述正极极片包含包括正极集流体以及设置于所述正极集流体至少一侧的正极活性材料层，其中所述正极活性材料为权利要求1至10中任意一项所述的正极活性材料，并且所述电池具有4.5V或更高的充电截止电压。
  14. 如权利要求13所述的钠离子电池，其中，所述电池在2.0-4.5V的电压下具有150mAh/g的首次放电比容量且在1C下100圈后具有80％或更高的容量保持率。
  15. 一种电池模块，其包括根据权利要求11或12中任一项或权利要求13或14中任一项所述的钠离子电池。
  16. 一种电池包，其包括根据权利要求15所述的电池模块。
  17. 一种装置，其包括根据权利要求11或12中任一项或权利要求13或14中任一项所述的钠离子电池，所述钠离子电池作为所述装置的电源或能量存储单元；可选地，所述装置包括电动车辆、混合动力电动车辆、插电式混合动力电动车辆、电动自行车、电动踏板车、电动高尔夫球车、电动卡车、电动船舶、储能系统。
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