Patent Application
20240282920
This application relates to a lithium-ion secondary battery, a battery module, a battery pack, and an electrical device.
During a first charge-discharge cycle of a lithium-ion secondary battery, a solid electrolyte interface (SEI) is formed on a surface of a negative electrode of the battery, thereby causing an irreversible loss of capacity, and in turn, reducing an energy density of the lithium-ion energy storage device. In a device that uses graphite as an negative electrode material, approximately 10% of an active lithium source is consumed in the first charge-discharge cycle. In a device that uses a high-specific-capacity negative electrode material such as an alloy (silicon or tin alloy or the like), an oxide (silicon oxide, tin oxide, or the like), or amorphous carbon, the consumption of the active lithium source is further increased. Therefore, fording an appropriate lithium supplementing method is of great significance to further increasing the energy density of the lithium-ion secondary battery.
For this purpose, a method for supplementing lithium for the negative electrode by using lithium powder such as stabilized lithium metal powder (SLMP, stabilized lithium metal powder) is put forward in the industry. However, although this method can increase the energy density of the battery, the lithium metal powder is of very high reactivity and is prone to react with moisture in the air, thereby posing a severe safety hazard. In a production process, a nonaqueous organic solvent that does not react with lithium is required to be used, and the control on moisture is also extremely stringent, thereby increasing the difficulty of the process.
In view of the great challenges encountered by the negative electrode lithium supplementation policy, a positive electrode lithium supplementation method is safer and easier to operate, and has drawn more and more attention from the industry. For example, Patent Document 1 discloses a positive electrode lithium-supplementing material based on a lithium-oxygen compound, a lithium source, and alkyl lithium. However, a decomposition potential of the lithium-containing compound in the material is relatively high, and oxygen and other by-products are generated in the decomposition process, thereby shortening the battery life.
In addition, known lithium-supplementing materials include a Li2NiO2 lithium-supplementing material. However, a very high content of free lithium exists on the surface of such a material, and is very prone to cause gelation of a slurry during mixing of the slurry, thereby drastically impairing the processability. In addition, during the first charging cycle, a large amount of active lithium is intercalated into the negative electrode, thereby leading to a further decrease in the true potential of the negative electrode. Moreover, this makes reduction reactions of the solvent in an electrolyte solution occur continuously on the negative electrode, thereby resulting in a continuous increase in impedance, and in turn, impairing the cycle performance of the battery.
This application is developed in view of the above situation, and an objective of this application is to provide a lithium-ion secondary battery capable of achieving a balanced high level of energy density, cycle life, C-rate performance, and the like.
To achieve the above objective, this application provides a lithium-ion secondary battery. The lithium-ion secondary battery includes a positive electrode plate, a negative electrode plate, a separator, and an electrolyte solution.
The positive electrode plate includes a positive current collector and a positive electrode material layer disposed on at least one surface of the positive current collector.
The positive electrode material layer includes a first positive electrode material represented by the following General Formula (1) and a second positive electrode material represented by the following General Formula (2).
The electrolyte solution includes vinylene carbonate.
A content of the vinylene carbonate based on a total mass of the electrolyte solution is greater than or equal to 0.1 wt % and less than or equal to 5 wt %.
Li1+xFeyMnzM1-y-zPO4-tAt (1)
(In General Formula (1), M includes one or more of Ti, Zr, V, or Cr; A includes one or more of S, N, F, Cl, or Br; and x, y, z, and t satisfy: −0.1≤x<0.1, 0<y≤1, 0≤z<1, 0<y+z≤1, and 0≤t<0.2.)
Li2+rNi0.5-pCu0.5-qTivNp+y-vO2-sBs (2)
(In General Formula (2), N includes one or more of Mn, Fe, Co, Al, V, Cr, or Nb; B includes one or more of S, N, F, Cl, or Br; and r, p, q, v, and s satisfy: −0.2≤r≤0.2, −0.5<p<0.5, −0.5<q<0.5, 0<v<0.01, 0≤p+q−v<0.2, and 0≤s<0.2)
As used in the positive electrode plate, the positive electrode material layer includes both the first positive electrode material and the second positive electrode material. The second positive electrode material forms a solid solution that exhibits a lower phase transformation energy barrier, a higher purity, and a higher specific capacity than an existing Li2NiO2 lithium-supplementing material. The second positive electrode material coordinates with the fast positive electrode material of an olivine structure to effectively improve the energy density, cycle life, and C-rate performance of the lithium-ion secondary battery. In addition, by adding a specified amount of vinylene carbonate additive into the electrolyte solution, the electrolyte solution can be synergistic with the first positive electrode material and the second positive electrode material of this application to form a more uniform and denser SEI film at the negative electrode after the first-cycle charging, thereby suppressing continuous loss of active lithium and further improving the cycle life of the lithium-ion secondary battery.
In some embodiments, in General Formula (2), p, q, and v satisfy: −0.1<p<0.1, −0.1<q<0.1, and 0.002≤v≤0.008. By making p, q, and v satisfy the specified ranges, the content of free lithium on the surface of the material can be further reduced, and the problem of gelation of the positive electrode slurry can be greatly alleviated, thereby achieving a more balanced high level of energy density, cycle life, and C rate performance.
In some embodiments, the positive electrode plate satisfies the following Formula (3):
0.5≤R·P/Q≤16 (3)
(In Formula (3), R represents a resistance of the positive electrode plate, in units of Ω; P represents a compaction density of the positive electrode plate, in units of g/cm3; and Q represents a single-side areal density of the positive electrode plate, in units of g/1540.25 mm2.)
By making the positive electrode plate satisfy Formula (3) above, the energy density, C-rate performance, and cycle life of the lithium-ion secondary battery can be further improved.
In some embodiments, the positive electrode plate further satisfies the following Formula (4):
1.5≤R·P/Q≤10 (4)
By making the positive electrode plate further satisfy Formula (4) above, the energy density, C-rate performance, and cycle life of the lithium-ion secondary battery can be even further improved.
In some embodiments, the resistance of the positive electrode plate satisfies: R≤3Ω, and optionally satisfies: R≤1Ω By making the resistance of the positive electrode plate fall within the specified range, the cycle performance and C-rate performance of the lithium-ion secondary battery are improved.
In some embodiments, the compaction density P of the positive electrode plate satisfies: 1.6<P<2.6 (in units of g/cm3). By making the compaction density P of the positive electrode plate fall within the specified range, the migration of electrons and ions in the positive electrode plate is facilitated, thereby improving the cycle performance of the lithium-ion secondary battery.
In some embodiments, the single-side areal density Q of the positive electrode plate satisfies: 0.16<Q<0.45 (in units of g/1540.25 mm2). By making the single-side areal density Q of the positive electrode plate fall within the specified range, the cycle performance and C-rate performance of the lithium-ion secondary battery can be improved at the same time as ensuring a high level of charge capacity and discharge capacity.
In some embodiments, a mass ratio between the first positive electrode material and the second positive electrode material is 5:1 to 99:1, and optionally 9:1 to 99:1. By making the mass ratio between the first positive electrode material and the second positive electrode material fall within the specified range, the first positive electrode material accounts for a larger proportion of the combination of the first positive electrode material and the second positive electrode material, and the positive electrode plate is of higher structural stability, thereby reducing capacity loss and impedance increase caused by structural disruption of the positive electrode material, and maintaining a high level of cycle stability and kinetic performance.
In some embodiments, in the positive electrode material layer, a percentage by weight of the first positive electrode material is 80 wt % to 98 wt %, and optionally 85 wt % to 98 wt %. By making the weight percent of the first positive electrode material in the positive electrode material layer fall within the specified range, the positive electrode plate is of even higher structural stability, thereby further reducing capacity loss and impedance increase caused by structural disruption of the positive electrode material, and improving the cycle stability and kinetic performance.
A crystal structure of the second positive electrode material belongs to an orthorhombic Immm space group.
In some embodiments, in an X-ray diffraction pattern of the second positive electrode material after first-cycle charging, a characteristic diffraction peak A is exhibited at 36° to 38°, a characteristic diffraction peak B is exhibited at 42° to 44°, and a characteristic diffraction peak C is exhibited at 62° to 64°.
A second aspect of this application provides a battery module. The battery module includes the secondary battery according to the first aspect of this application.
A third aspect of this application provides a battery pack. The battery pack includes the battery module according to the second aspect of this application.
A fourth aspect of this application provides a device. The device includes at least one of the secondary battery according to the first aspect of this application, the battery module according to the second aspect of this application, or the battery pack according to the third aspect of this application.
The battery module, the battery pack, and the device of this application each include the secondary battery according to this application, and therefore, exhibit at least the same advantages as the secondary battery.
To make the objectives, technical solutions, and advantages of this application clearer, the following describes some embodiments of this application in detail with reference to accompanying drawings. However, a person of ordinary skill in the art understands that such embodiments are just intended to expound rather than limit the technical solutions hereof. Any and all modifications, equivalent replacements, improvements, and the like made without departing from the essence and principles of this application still fall within the protection scope of this application.
For brevity, some specific numerical ranges are disclosed herein. However, any lower limit may be combined with any upper limit to form an unspecified range, any lower limit may be combined with any other lower limit to form an unspecified range, and any upper limit may be combined with any other upper limit to form an unspecified range. In addition, although not explicitly stated, any point and any single numerical value between end points of a range are included in the range. In addition, each separately disclosed point or single numerical value may be used as a lower limit or upper limit to combine with any other point or other single numerical value or with any other lower or upper limit to form an unspecified range.
It is hereby noted that in the description herein, unless otherwise specified, a range defined by a numerical value qualified by “at least” or “at most” includes this numerical value, and the word “more” in the phrase “one or more of” means at least two.
The above summary of this application is not intended to describe every disclosed embodiment or every implementation of this application. The following description exemplifies illustrative embodiments in more detail. In several places throughout this application, guidance is provided through a series of embodiments. The embodiments may be used in various combinations. In each instance, an enumerated list serves merely as a representative list, but is not to be construed as an exclusive list.
To solve the above problems in the prior art, after in-depth research the applicant hereof finds that: by compounding the existing Li2NiO2 lithium-supplementing material with Cu, Ti, and other optional metal elements, the second positive electrode material forms a solid solution that exhibits a lower phase transformation energy barrier, a higher purity, and a higher specific capacity than the existing Li2NiO2 lithium-supplementing material. The second positive electrode material coordinates with the first positive electrode material of an olivine structure to make following improvements: on the one hand, the loss of active lithium caused by the formation of the SEI film is compensated for effectively during file-cycle charging of the battery by virtue of the second positive electrode material characterized by a high first-charge specific capacity and a low initial Coulombic efficiency. During the first discharge, sufficient lithium ions are intercalated back into the first positive electrode material, thereby increasing the energy density of the battery effectively. On the other hand, the first positive electrode material of an olivine structure in this application is structurally stable, little changes in volume during charging and discharging, and is excellent in cycle stability. Further, the applicant hereof finds that, by adding a specified amount of vinylene carbonate into the electrolyte solution, the electrolyte solution can be synergistic with the positive electrode plate containing the first positive electrode material and the second positive electrode material, so as to form a more uniform and denser SEI film at the negative electrode after the first-cycle charging, thereby suppressing continuous loss of active lithium and further improving the cycle life of the lithium-ion secondary battery. Therefore, the lithium-ion secondary battery according to this embodiment achieves a high energy density, good C-rate performance, and a long cycle life.
Specifically, this application relates to a lithium-ion secondary battery. The lithium-ion secondary battery includes a positive electrode plate, a negative electrode plate, a separator, and an electrolyte solution. The positive electrode plate includes a positive current collector and a positive electrode material layer disposed on at least one surface of the positive current collector.
The positive electrode material layer includes a first positive electrode material represented by the following General Formula (1) and a second positive electrode material represented by the following General Formula (2):
The electrolyte solution includes vinylene carbonate.
A content of the vinylene carbonate based on a total mass of the electrolyte solution is greater than or equal to 0.1 wt % and less than or equal to 5 wt %.
Li1+xFeyMnzM1-y-zPO4-tAt (1)
(In General Formula (1), M includes one or more of Ti, Zr, V, or Cr; A includes one or more of S, N, F, Cl, or Br; and x, y, z, and t satisfy: −0.1≤x<0.1, 0<y≤1, 0≤z<1, 0<y+z≤1, and 0≤t<0.2.)
Li2+rNi0.5-pCu0.5-qTivNp+y-vO2-sBs (2)
(In General Formula (2), N includes one or more of Mn, Fe, Co, Al, V, Cr, or Nb; B includes one or more of S, N, F, Cl, or Br; and r, p, q, v, and s satisfy: −0.2≤r≤0.2, −0.5<p<0.5, −0.5<q<0.5, 0<v<0.01, 0≤p+q−v<0.2, and 0≤s<0.2)
A lithium-ion battery, a battery module, a battery pack, and an electrical device of this application are described in detail below with due reference to drawings.
A lithium-ion secondary battery is a battery that is reusable through activation of an active material in the lithium-ion battery by charging the battery that has been discharged. Generally, a lithium-ion secondary battery includes a positive electrode plate, a negative electrode plate, a separator, and an electrolyte solution. In a charge-and-discharge cycle of the battery, active ions are shuttled between the positive electrode plate and the negative electrode plate by intercalation and deintercalation. Disposed between the positive electrode plate and the negative electrode plate, the separator can isolate electrons to prevent an internal short circuit while allowing active ions to pass through the separator and move between the positive electrode and the negative electrode. The separator serves a separation function. The electrolyte solution serves to conduct ions between the positive electrode plate and the negative electrode plate.
A positive electrode plate includes a positive current collector and a positive electrode material layer disposed on at least one surface of the positive current collector. As an example, the positive current collector includes two surfaces opposite to each other in a thickness direction of the current collector. The positive electrode material layer is disposed on any one or both of the two opposite surfaces of the positive current collector.
The positive electrode material layer includes a first positive electrode material represented by the following General Formula (1) and a second positive electrode material represented by the following General Formula (2):
Li1+xFeyMnzM1-y-zPO4-tAt (1)
(In General Formula (1), M includes one or more of Ti, Zr, V, or Cr; A includes one or more of S, N, F, Cl, or Br; and x, y, z, and t satisfy: −0.1≤x<0.1, 0<y≤1, 0≤z<1, 0<y+z≤1, and 0≤t<0.2.)
Li2+rNi0.5-pCu0.5-qTivNp+y-vO2-sBs (2)
(In General Formula (2), N includes one or more of Mn, Fe, Co, Al, V, Cr, or Nb; B includes one or more of S, N, F, Cl, or Br; and r, p, q, v, and s satisfy: −0.2≤r≤0.2, −0.5<p<0.5, −0.5<q<0.5, 0<v<0.01, 0≤p+q−v<0.2, and 0≤s<0.2)
By letting the positive electrode material layer include both the first positive electrode material and the second positive electrode material, the lithium-ion secondary battery achieves a high energy density, good C-rate performance, and a long cycle life.
In general formula (1), x satisfies −0.1≤x<0.1. To further reduce the volume change during charging and discharging and further improve the cycle stability of the battery, x preferably falls within: −0.1≤x≤0.05, and more preferably falls within: −0.05≤x≤0. In addition, y satisfies: 0<y≤1. To further improve the cycle stability of the battery, y preferably falls within: 0.5≤y≤1, and more preferably falls within: 0.5≤y≤0.95. Moreover, z satisfies: 0≤z<1. To improve the cycle stability of the battery, z preferably falls within: 0≤z≤0.5, and more preferably falls within: 0.025≤z≤0.45.
In General Formula (1), M is one or more selected from Ti, Zr, V, or Cr. To be synergistic with the second positive electrode material and increase the energy density and cycle life of the lithium-ion secondary battery, M is preferably one or more selected from Ti, Zr, or V. and more preferably one or more selected from Ti or Zr. In addition, A includes one or more of S, N, F, Cl, or Br. To maintain excellent overall performance, A is preferably one or more selected from F, Cl, or Br, and more preferably is F. Moreover, t satisfies: 0≤t<0.2. To maintain excellent overall performance, t preferably falls within: 0≤t≤0.05.
In General Formula (1), y+z satisfies: 0<y+z≤1. To be synergistic with the second positive electrode material and increase the energy density and cycle life of the lithium-ion secondary battery, y+z preferably falls within: 0.95≤y+z≤1.
In General Formula (2), r satisfies: −0.2≤r≤0.2. To effectively compensate for the loss of active lithium caused by the formation of the SEI film and further increase the energy density of the battery, r preferably falls within: −0.05≤r≤0.2, and more preferably falls within: 0≤r≤0.2. In addition, p satisfies: −0.5<p<0.5. To further increase the energy density of the battery, p preferably falls within: −0.1<p<0.1, more preferably falls within: −0.046≤p≤0.058, and even more preferably falls within: 0.002≤p≤0.054. Moreover, q satisfies: −0.5<q<0.5. To effectively increase the energy density and cycle life of the battery, q preferably falls within: −0.1<q<0.1, more preferably falls within: −0.046≤q≤0.058, and even more preferably falls within: 0.002≤q≤0.054. Further, v satisfies: 0<v<0.01. To more effectively reduce the content of free lithium on the surface of the material, and more effectively alleviate the problem of gelation of the positive electrode slurry, and effectively increase the energy density of the battery, v preferably falls within: 0.002≤v≤0.008, and more preferably falls within: 0.004≤v≤0.008. Further, s satisfies: 0≤s<0.2. To improve the cycle performance and energy density of the battery, s preferably falls within: 0≤s≤0.1, and more preferably falls within: 0≤s≤0.05.
In General Formula (2), N includes one or more of Mn, Fe, Co, Al, V. Cr, or Nb. To improve the C rate performance and the cycle performance of the battery, N is preferably one or more selected from Mn, Fe, Co, or Cr, and more preferably one or more selected from Mn or Co. In addition, B includes one or more of S, N, F, Cl, or Br. To maintain excellent overall performance, B is preferably one or more selected from F, Cl, or Br, and more preferably is F.
In General Formula (2), p+q−v satisfies: 0≤p+q−v<0.2. To improve the C-rate performance and cycle performance of the battery, p+q−v preferably satisfies: 0≤p+q−v≤0.1.
In some embodiments, the positive electrode plate satisfies the following Formula (3):
0.5≤R·P/Q≤16 (3)
(In Formula (3), R represents a resistance of the positive electrode plate, in units of Ω; P represents a compaction density of the positive electrode plate, in units of g/cm3; and Q represents a single-side areal density of the positive electrode plate, in units of g/1540.25 mm2.)
By making the positive electrode plate satisfy Formula (3) above, the energy density, C-rate performance, and cycle life of the lithium-ion secondary battery can be further improved.
In some embodiments, preferably, the positive electrode plate further satisfies the following Formula (4):
1.5≤R·P/Q≤10 (4)
It is hereby noted that in this application, the calculation of R·P/Q involves only numerical calculation. For example, if the resistance R of the positive electrode is 0.5Ω, the compaction density P is 2.2 g/cm3, and the single-side areal density Q of the positive electrode is 0.3 g/1540.25 mm2, then R·P/Q=3.7.
In some embodiments, the resistance of the positive electrode plate satisfies: R≤3Ω, and preferably satisfies: R≤1Ω By making the resistance of the positive electrode plate fall within the specified range, the cycle performance and C-rate performance of the lithium-ion secondary battery are prevented from being deteriorated by an excessive resistance of the positive electrode plate, thereby improving the cycle performance and C-rate performance of the lithium-ion secondary battery. In this application, the resistance R of the positive electrode plate is a value measured by using a direct-current two-probe method. The contact area between the probe and the positive electrode plate is 49 πmm2. As an example, the upper and lower sides of the positive electrode plate are clamped between two conductive terminals (with a diameter of 14 mm) of an electrode plate resistance tester (Hioki BT23562 internal resistance tester manufactured by Hioki E.E. Corporation), and a pressure of 15 MPa to 27 MPa is applied to hold the electrode plate in place, so that the resistance of the positive electrode plate is measured by using the electrode plate resistance tester.
In some embodiments, the compaction density P of the positive electrode plate satisfies: 1.6<P<2.6 (in units of g/cm3). By making the compaction density P of the positive electrode plate fall within the specified range, the cycle performance and C-rate performance of the battery are prevented from being deteriorated, thereby facilitating the migration of electrons and ions in the positive electrode plate, and improving the cycle performance of the lithium-ion secondary battery. In this application, the compaction density P of the positive electrode may be calculated by a formula P=m/v, where m is the mass of the positive electrode material layer in units of g, and v is the volume of the positive electrode material layer in units of cm3. The volume v of the positive electrode material layer may be a product of the area Ar of the positive electrode material layer and the thickness of the positive electrode material layer.
In some embodiments, the single-side areal density Q of the positive electrode plate satisfies: 0.16<Q<0.45 (in units of g/1540.25 mm2). By making the single-side areal density Q of the positive electrode plate fall within the specified range, an excessive single-side areal density of the positive electrode plate is avoided so as not to reduce the cycle life of the battery, impair the C-rate performance of the battery, or reduce the discharge capacity of the battery at a high C-rate; and a deficient single-side areal density of the positive electrode plate is avoided so as not to increase the lengths of the current collector and the separator or increase the internal resistance of the battery while achieving the same capacity of the battery, thereby improving the cycle performance and C-rate performance of the lithium-ion secondary battery while ensuring a high level of charge capacity and discharge capacity. In this application, the single-side areal density Q of the positive electrode plate may be calculated by a formula Q=1540.25 m/Ar, where m is the mass of the positive electrode material layer, in units of g, and Ar is the area of the positive active material layer, in units of mm2.
In some embodiments, a mass ratio between the first positive electrode material and the second positive electrode material is 5:1 to 99:1, preferably 9:1 to 99:1, and more preferably 10:1 to 48:1. By making the mass ratio between the fast positive electrode material and the second positive electrode material fall within the specified range, the first positive electrode material accounts for a larger proportion of the combination of the first positive electrode material and the second positive electrode material, and the positive electrode plate is of higher structural stability, thereby reducing capacity loss and impedance increase caused by structural disruption of the positive electrode material, and maintaining a high level of cycle stability and kinetic performance.
In some embodiments, in the positive electrode material layer, a percentage by weight of the first positive electrode material is 80 wt % to 98 wt %, and preferably 85 wt % to 98 wt %. By making the weight percent of the first positive electrode material in the positive electrode material layer fall within the specified range, the positive electrode plate is of even higher structural stability, thereby further reducing capacity loss and impedance increase caused by structural disruption of the positive electrode material, and improving the cycle stability and kinetic performance.
In some embodiments, the crystal structure of the second positive electrode material belongs to an orthorhombic Immm space group. In some embodiments, in an X-ray diffraction pattern of the second positive electrode material after first-cycle charging, a characteristic diffraction peak A is exhibited at 36° to 38°, a characteristic diffraction peak B is exhibited at 42° to 44°, and a characteristic diffraction peak C is exhibited at 62° to 64°.
To the extent that the effect of this application is not impaired, the positive electrode material layer of this application may include other positive electrode materials such as lithium transition metal oxide in addition to the first positive electrode material and the second positive electrode material.
The positive electrode material layer of this application optionally includes a binder and a conductive agent. The types of the conductive agent and binder are not particularly limited herein, and may be selected according to actual needs.
As an example, the binder may include one or more of styrene-butadiene rubber (SBR), water-based acrylic resin (water-based acrylic resin), carboxymethyl cellulose (CMC), polyvinylidene difluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), poly(ethylene-co-vinyl acetate) (EVA), or polyvinyl alcohol (PVA). The conductive agent may include one or more of graphite, superconductive carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, or carbon nanofibers.
In some embodiments, the mass percent of the conductive agent in the positive electrode material layer is 0.5 wt % or above. By setting the mass percent of the conductive agent to fall within the above range, a relatively low resistance of the positive electrode plate can be achieved.
In some embodiments, the mass percent of the binder in the positive electrode material layer is 2.5 wt % or below. By setting the mass percent of the binder to fall within the above range, a relatively low resistance of the positive electrode plate can be achieved.
In the lithium-ion secondary battery of this application, the positive current collector may be a metal foil, a porous metal sheet, or a composite current collector. For example, the metal foil or porous metal sheet may be a foil or a porous sheet of metals such as aluminum, copper, nickel, titanium, silver, or an alloy thereof, and preferably an aluminum foil. The composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector may be formed by overlaying the polymer material substrate with a metal material (for example, aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, or silver alloy). The polymer material substrate may be, for example, polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), or polyethylene (PE). The thickness of the positive current collector is 5 μm to 20 μm, and preferably, 6 μm to 18 μm, and more preferably, 8 μm to 16 μm.
The positive electrode plate of this application may be prepared by a conventional method in this field. Specifically, the positive electrode plate may be prepared by the following method: dispersing the constituents of the positive electrode plate such as the first positive electrode material, the second positive electrode material, an optional conductive agent, an optional binder, and any other constituents into a solvent (such as N-methyl-pyrrolidone) to form a positive electrode slurry; coating a positive current collector with the positive electrode slurry, and performing steps such as oven-drying and cold pressing to obtain a positive electrode plate. Alternatively, the positive electrode plate may be manufactured by the following method: tape-casting a positive electrode slurry, which is prepared for forming a positive electrode material layer, onto a separate carrier, and then pressing a film, which is stripped off from the carrier, onto the positive current collector. In addition, in the above embodiment, the positive electrode slurry is prepared by directly mixing the first positive electrode material and the second positive electrode material. However, the slurry preparation method is not limited to this, but may be: blending the second positive electrode material separately to produce a slurry, and applying the slurry onto the upper or lower layer of the first positive electrode material.
In the lithium-ion secondary battery, the negative electrode plate typically includes a negative current collector and a negative electrode material layer disposed on at least one surface of the negative current collector. For example, the negative current collector includes two surfaces opposite to each other in a thickness direction of the current collector. The negative electrode material layer is disposed on either or both of the two opposite surfaces of the negative current collector.
In the lithium-ion secondary battery of this application, the negative current collector may be a metal foil, a porous metal sheet, a composite current collector, or made of other materials. For example, the metal foil or porous metal sheet may be a foil or a porous sheet of metals such as copper, nickel, titanium, iron, or an alloy thereof, and preferably a copper foil. The composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector may be formed by overlaying the polymer material substrate with a metal material (for example, copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, or silver alloy). The polymer material substrate may be, for example, polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), or polyethylene (PE).
In the lithium-ion secondary battery of this application, the negative electrode material layer typically includes a negative electrode material, and optionally, a conductive agent, a binder, and a thickener.
The negative electrode material may be a negative electrode material commonly used for preparing a negative electrode of a lithium-ion secondary battery in this field. For example, the negative electrode material may be one or more of natural graphite, artificial graphite, mesocarbon microbead (MCMB), hard carbon, soft carbon, silicon, a silicon-carbon composite, SiO, a Li—Sn alloy, a Li—Sn—O alloy, Sn, SnO, SnO2, spinel-structured lithium titanium oxide Li4Ti5O12, a Li—Al alloy, or metallic lithium.
As an example, the conductive agent may include one or more of graphite, superconductive carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, or carbon nanofibers.
As an example, the binder may include one or more of styrene-butadiene rubber (SBR), polyvinylidene difluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), water-based acrylic resin (water-based acrylic resin), or carboxymethyl cellulose (CMC).
As an example, the thickener may be carboxymethyl cellulose (CMC) or the like.
This application is not limited to such materials. This application may use other materials in addition to the materials that can be used as a negative electrode material, a conductive agent, a binder, and a thickener of a lithium-ion secondary battery.
The negative electrode plate of this application may be prepared by a conventional method in this field. Specifically, a method for preparing the negative electrode plate includes: dispersing the negative electrode material and optionally the conductive agent, binder, and thickener in a solvent to form a homogeneous negative electrode slurry, coating a negative current collector with the negative electrode slurry, and performing steps such as oven-drying and cold pressing to obtain a negative electrode. The solvent may be N-methyl-pyrrolidone (NMP), deionized water, or the like.
The electrolyte solution of this application includes an organic solvent, an electrolyte lithium salt, and an additive. The types of the organic solvent and the electrolyte lithium salt are not particularly limited herein, and may be selected according to actual needs.
As an example, the solvent may be one or more, and preferably at least two, selected from ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethylene propyl carbonate (EPC), butylene carbonate (BC), fluoroethylene carbonate (FEC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), methyl sulfonyl methane (MSM), ethyl methyl sulfone (EMS), or (ethylsulfonyl)ethane (ESE).
As an example, the electrolyte lithium salt may be one or more selected from lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium bisfluorosulfonimide (LiFSI), lithium bistrifluoromethanesulfonimide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluoro(oxalato) borate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium difluorophosphate (LiPO2F2), lithium difluoro(bisoxalato)phosphate (LiDFOP), or lithium tetrafluoro(oxalato)phosphate (LiTFOP).
The electrolyte solution of this application includes vinylene carbonate (VC) as an additive. A content of the vinylene carbonate based on a total mass of the electrolyte solution is greater than or equal to 0.1 wt % and less than or equal to 5 wt %. By adding a specified amount of vinylene carbonate as an additive into the electrolyte solution, the electrolyte solution can be synergistic with the positive electrode plate containing the first positive electrode material and the second positive electrode material, so as to form a more uniform and denser SEI film at the negative electrode after the first-cycle charging, thereby suppressing continuous loss of active lithium and further improving the cycle life of the lithium-ion secondary battery.
The electrolyte solution further optionally includes other additives. Without being limited herein, the types of other additives may be any additive suitable for use in a lithium-ion secondary battery and may be selected according to actual needs. As an example, the additives may include one or more of vinyl ethylene carbonate (VEC), succinonitrile (SN), adiponitrile (AND), 1,3-propene sultone (PST), sulfonate cyclic quaternary ammonium salt, tris(trimethylsilane)phosphate (TMSP), or tris(trimethylsilane)borate (TMSB).
The electrolyte solution may be prepared by a conventional method in this field. Specifically, the electrolyte solution may be obtained by mixing well an organic solvent, an electrolyte lithium salt, vinylene carbonate, and other optional additives. Specific order of adding the materials is not particularly limited. For example, the electrolyte solution may be obtained by adding an electrolyte lithium salt, vinylene carbonate, and other optional additives into an organic solvent and mixing the materials well. As an example, the electrolyte lithium salt is added into the organic solvent first, and then the vinylene carbonate and other optional additives are separately or simultaneously added into the organic solvent.
The type of the separator is not particularly limited herein, and may be any well-known porous separator that is stable both electrochemically and chemically for use in a lithium-ion secondary battery. For example, the separator may be a glass fiber film, non-woven fabric film, polyethylene film, polypropylene film, polyvinylidene difluoride film, or a multilayer composite film that contains one or at least two thereof, or any combination thereof.
In some embodiments, a method for preparing the lithium-ion secondary battery is: stacking the positive electrode plate, the separator, and the negative electrode plate in sequence to obtain an electrode assembly in which the separator is located between the positive electrode plate and the negative electrode plate to serve a separation function; and then placing the electrode assembly into an outer package, injecting an electrolyte solution, and sealing the package to obtain a lithium-ion secondary battery. The electrode assembly may be obtained by, instead of the stacking process, a winding process in which the positive electrode plate, the separator, and the negative electrode plate are wound.
In some embodiments, the outer package of the lithium-ion secondary battery may be a hard shell such as a hard plastic shell, an aluminum shell, a steel shell, or the like. Alternatively, the outer package of the lithium-ion secondary battery may be a soft package such as a pouch-type soft package. The material of the soft package may be plastic such as one or more of polypropylene (PP), polybutylene terephthalate (PBT), or polybutylene succinate (PBS).
The shape of the lithium-ion secondary battery is not particularly limited in this application, and may be cylindrical, prismatic or any other shape.
In some embodiments, referring to
In some embodiments, the lithium-ion secondary battery may be assembled to form a battery module. The battery module may contain a plurality of secondary batteries, and the specific number of secondary batteries in a battery module may be adjusted according to practical applications and capacity of the battery module.
Optionally, the battery module 4 may further include a shell that provides an accommodation space. The plurality of secondary batteries 5 are accommodated in the accommodation space.
In some embodiments, the battery module may be assembled to form a battery pack. The number of the battery modules contained in a battery pack may be adjusted according to practical applications and the capacity of the battery pack.
Another aspect of this application provides a device. The device includes at least one of the lithium-ion secondary battery, the battery module, or the battery pack according to this application. The lithium-ion secondary battery may be used as a power supply of the device, or used as an energy storage unit of the device. The device may be, but is not limited to, a mobile device (such as a mobile phone or a laptop computer), an electric vehicle (such as a battery electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, or an electric truck), an electric train, a ship, a satellite system, or an energy storage system.
Depending on the use requirements of the device, the lithium-ion secondary battery, battery module, or battery pack may be selected for use in the device.
As an example, the device may be a mobile phone, a tablet computer, a laptop computer, or the like. The device is generally required to be thin and light, and may use a lithium-ion secondary battery as a power supply.
The following describes some embodiments of this application. The embodiments described below are illustrative, and are merely intended to construe this application but not to limit this application. Unless techniques or conditions are otherwise expressly specified in an embodiment hereof, the techniques or conditions described in the literature in this field or in an instruction manual of the product are applicable in the embodiment. A reagent or instrument used herein without specifying a manufacturer is a conventional product that is commercially available in the market.
Dissolving a first positive electrode material LiFePO4, a second positive electrode material Li2Ni0.498Cu0.498Ti0.002O2, a binder polyvinylidene difluoride (PVDF), a conductive agent carbon black at a mass ratio of 92.4:4.0:2.1:1.5 in an N-methyl-pyrrolidone (NMP) solvent, and vacuum-mixing the mixture thoroughly until the mixture becomes a homogeneous transparent system to obtain a positive electrode slurry. Subsequently, coating a positive current collector aluminum foil with the positive electrode slurry evenly, transferring the coated current collector into an oven to dry the slurry at 120° C., and then performing cold pressing and slitting to obtain a positive electrode. In the positive electrode material layer, the mass percent of the first positive electrode material LiFePO4 is 92.4%, and the mass percent of the second positive electrode material Li2Ni0.498Cu0.498 Ti0.002O2 is 4.0%.
Dissolving artificial graphite as a negative electrode material, sodium carboxymethyl cellulose (CMC-Na) as a thickener, styrene-butadiene rubber (SBR), and carbon black as a conductive agent at a mass ratio of 95.7:1.0:1.8:1.5 in deionized water, and mixing the mixture well with a vacuum mixer to obtain a negative electrode slurry. Subsequently, coating a negative current collector copper foil with the negative electrode slurry evenly, transferring the current collector into an oven to dry the slurry at 120° C., and then performing cold pressing and slitting to obtain a negative electrode plate.
Mixing ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) at a volume ratio of 1:1:1, and stirring the mixture well to obtain an organic solvent. Dissolving 1 mol/L LiPF6 in the organic solvent, and then adding 3 wt % vinylene carbonate (VC), and stirring well to obtain an electrolyte solution, where the mass percent of the vinylene carbonate is a percentage by weight based on the total mass of the electrolyte solution.
(4) Preparing a Separator: Using a 14 μm-Thick Polypropylene Film (Manufactured by Celgard) as a separator.
Stacking the positive electrode plate, the separator, and the negative electrode plate in sequence in such a way that the separator is located between the positive electrode plate and the negative electrode plate to serve a separation function, and then winding the stacked structure to form an electrode assembly; welding tabs to the electrode assembly, placing the electrode assembly into a shell, injecting the electrolyte solution and sealing the opening, and then performing steps such as static standing, chemical formation, and shaping to obtain a lithium-ion secondary battery.
The lithium-ion secondary battery is prepared in the same way as in Embodiment 1 except that the type of the first positive electrode material, the type of the second positive electrode material, and the content of the vinylene carbonate in the electrolyte solution are changed according to Table 1.
A performance test is performed by the following methods on the lithium-ion secondary batteries prepared in the above embodiments and comparative embodiments, and the test results obtained are shown in Table 1.
Charging a lithium-ion secondary battery at a constant current of 1 C rate at 60° C. until the voltage reaches 4.2 V, and then charging the battery at a constant voltage until the current is less than or equal to 0.05Ω, and then discharging the battery at a constant current of 1 C until the voltage drops to 2.5 V, thereby completing one charge-discharge cycle. Recording the first-cycle discharge capacity of the lithium-ion secondary battery. Repeating the charge-discharge cycle for the lithium-ion secondary battery according to the foregoing steps, and recording the discharge capacity at the end of each cycle until the discharge capacity of the lithium-ion secondary battery fades to 80% of the first-cycle discharge capacity. Recording the number of charge-discharge cycles.
Charging a lithium-ion secondary battery at a constant current rate of 0.5Ω at 25° C. until the voltage reaches 4.2 V, and then charging the battery at a constant voltage until the current is less than or equal to 0.05Ω, and then discharging the battery at a constant current rate of 0.5Ω until the voltage reaches 2.5 V, and recording the 0.5C-rate discharge capacity.
Charging the lithium-ion secondary battery at a constant current rate of 0.5Ω at 25° C. until the voltage reaches 4.2 V, and then charging the battery at a constant voltage until the current is less than or equal to 0.05Ω, and then discharging the battery at a constant current rate of 2° C. until the voltage reaches 2.5 V, and recording the 2C-rate discharge capacity.
Subsequently, calculating, by using the following formula, the 2 C-rate discharge capacity retention rate (%) of the lithium-ion secondary battery to characterize the C-rate performance (%) of the battery.
2 C-rate discharge capacity retention rate of the lithium-ion secondary battery (%)=2 C-rate discharge capacity/0.5 C-rate discharge capacity×100%.
Charging a lithium-ion secondary battery at a constant current rate of 0.2 C at 25° C. until the voltage reaches 4.2 V. and then charging the battery at a constant voltage until the current is less than or equal to 0.05Ω. Subsequently, leaving the battery to stand for 30 minutes, and then discharging the battery at a constant current rate of 0.2 C until the voltage reaches 2.5 V, and recording the 0.2 C-rate discharge capacity of the secondary lithium-ion battery as D0 (Ah), and recording the discharge plateau as V0 (V). Weighing the lithium-ion battery and recording the weight as m0 (kg). Subsequently, calculating the energy density of the lithium-ion secondary battery (unit: Wh/Kg) by using the following formula:
Energy density=D0×V0/m0.
Charging the lithium-ion secondary battery, which is prepared in Embodiment 1, at a constant current rate of 1 C at 25° C. until the voltage reaches 4.2 V, and then charging the battery at a constant voltage until the current is less than or equal to 0.05Ω. Disassembling the lithium-ion secondary battery charged for a first cycle, and taking out the positive electrode plate. Testing the positive electrode plate by using an X-ray diffractometer, and observing the resultant XRD pattern of the positive electrode plate after the first-cycle charging, as shown in
As can be seen from
As can be seen from Table 1 above, in Embodiments 1 to 21 in which the positive electrode material layer includes both the first positive electrode material and the second positive electrode material of this application, the lithium-ion secondary battery achieves a high energy density, good C-rate performance, and a long cycle life concurrently. By contrast, in Comparative Embodiments 1 to 5 in which the positive electrode material layer does not include the first positive electrode material or the second positive electrode material of this application, the energy density of the lithium-ion secondary battery is decreased, and the number of high-temperature cycles of the battery is reduced. Further, by adding a specified amount of vinylene carbonate as an additive into the electrolyte solution, a denser and thinner SEI film is induced to be generated, thereby preventing continuous consumption of the electrolyte solution, and further improving the cycle life of the lithium-ion secondary battery.
Similar to the preparation method in Embodiment 1 except the differences shown in Table 2 below.
In addition, the performance of the prepared lithium-ion secondary battery is tested by the foregoing battery performance test method. The test results are shown in Table 2.
Further, the film resistance of the positive electrode plate is measured by the method to be described below. Moreover, the compaction density and single-side areal density of the positive electrode plate are calculated by the method to be described below.
Measuring the resistance of the positive electrode plate by using a Hioki BT3562 resistance tester. Specifically, clamping the positive electrode plate between two conductive terminals (14 mm in diameter) of the internal resistance tester, and applying a pressure of 15 MPa to 27 MPa to fix the electrode plate, and measuring the resistance R of the positive electrode plate by sampling the resistance values at intervals of 5 s to 17 s.
Calculating the compaction density P of the positive electrode by using a formula P=m/v, where m is the mass of the positive electrode material layer in units of g, and v is the volume of the positive electrode material layer in units of cm3. The volume v of the positive electrode material layer is obtained by calculating a product of the area Ar of the positive electrode material layer and the thickness of the positive electrode material layer.
The single-side areal density Q of the positive electrode plate is calculated by a formula Q=1540.25 m/Ar, where m is the mass of the positive electrode material layer, in units of g, and Ar is the area of the positive active material layer, in units of mm2.
As can be seen from Table 2 above, by making the positive electrode plate satisfy 0.5≤R·P/Q≤16, the energy density, C-rate performance, and cycle life of the lithium-ion secondary battery can be further improved. In addition, by making the positive electrode plate further satisfy 1.5≤R·P/Q≤10, the energy density, C-rate performance, and cycle life of the lithium-ion secondary battery can be even further improved.
A person of ordinary skill in the art understands that the embodiments described above are merely a part of exemplary embodiments for implementing this application. In practical applications, a variety of variations and modifications may be made in form and detail to the embodiments, and such variations and modifications still fall within the protection scope of this application.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/126213 | Oct 2021 | WO | international |
This application is a continuation application of PCT/CN2021/131275, filed on Nov. 17, 2021, which claims priority of international application No. PCT/CN2021/126213, filed on Oct. 25, 2021, the disclosure of which is hereby incorporated by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2021/131275 | Nov 2021 | WO |
| Child | 18644696 | US |
