Patent Application
20230170472
The present application relates to the technical field of lithium batteries, and in particular to a positive electrode plate, a secondary battery, a battery module, a battery pack and a power consuming device.
Lithium-ion batteries are widely used in electric vehicles and consumer electronics because of their advantages such as a high energy density, high output power, long cycle life and low environmental pollution. Among them, the application of lithium iron phosphate batteries is expanding, and its market share is increasing year by year.
However, the conductivity of a lithium iron phosphate material is relatively weak, and this characteristic becomes more prominent at a low temperature, which is caused by inherent defects in the olivine crystal structure of the lithium iron phosphate material. Due to the performance weakness of a lithium iron phosphate material, the capacity and working voltage performance of a lithium iron phosphate battery become worse at a low temperature, and the discharge power is limited and reduced. It can be seen that the energy density of a lithium ion battery is significantly affected by a temperature.
The present application has been made in view of the above problems, and an objective thereof is to improve the performance of secondary batteries at a low temperature.
In order to achieve the above objective, the present application provides a positive electrode plate, a secondary battery, a battery module, a battery pack and a power consuming device.
A first aspect of the present application provides a positive electrode plate, including a current collector, a first positive electrode active material layer and a second positive electrode active material layer, wherein the second positive electrode active material layer is arranged between the current collector and the first positive electrode active material layer, or the first positive electrode active material layer is arranged between the current collector and the second positive electrode active material layer; the first positive electrode active material layer comprises a first positive electrode active material, a first binder and a first conductive agent, wherein the first positive electrode active material is selected from at least one of LiqCoO2, Li1+xCo1−y−zNiyMnzO2 or carbon-coated LiβFeαM(1−α)PO4, wherein 0≤q≤1, 0≤x≤0.1, 0≤y≤0.95, 0≤z≤0.95, 0.2≤α≤1, 1≤β≤1.1, and M is selected from at least one of Cu, Mn, Cr, Zn, Pb, Ca, Co, Ni and Sr; and the second positive electrode active material layer comprises a second positive electrode active material, a second binder and a second conductive agent, wherein the second positive electrode active material is selected from carbon-coated LiβFeαM(1−α)PO4, where 0.2≤α≤1, 1≤β≤1.1, M is selected from at least one of Cu, Mn, Cr, Zn, Pb, Ca, Co, Ni, and Sr, and the second positive electrode active material has a diffraction peak A between 29° and 30° in the X-ray diffraction pattern, and a diffraction peak B between 25° and 26°, and the intensity ratio IA/IB of the diffraction peaks satisfies: 0.98≤IA/IB≤1.1, optionally 1.05≤IA/IB≤1.1.
Thus, in some embodiments of the present application, the low temperature performance of a secondary battery is improved by means of the synergistic effect between the first positive electrode active material layer and the second active material layer in the positive electrode plate.
In one embodiment, the thickness D2 of the second positive electrode active material layer is 2 μm to 40 μm, optionally 10 μm to 30 μm, and further optionally 15 μm to 25 μm. By controlling the thickness of the second positive electrode active material layer, it is beneficial to the improvement of the capacity retention rate and power performance of a secondary battery under low temperature conditions.
In one embodiment, the average particle size of the primary particles of the second positive electrode active material is 20 nm to 240 nm, optionally 20 nm to 160 nm, further optionally 20 nm to 80 nm. By controlling the average particle size of the primary particles of the second positive electrode active material, the migration rate of lithium ions in the positive electrode active material can be improved, which is beneficial to the improvement of the capacity retention rate and power performance of the secondary battery under low temperature conditions.
In one embodiment, based on the total mass of the second positive electrode active material layer, the contents of the second positive electrode active material, the second binder and the second conductive agent are 80% to 98%, 1% to 10% and 1% to 10%, respectively. By controlling the contents of the second positive electrode active material, the second binder and the second conductive agent in the second positive electrode active material layer, it is beneficial to the improvement of the capacity retention rate and power performance of the secondary battery under low temperature conditions.
In one embodiment, the thickness D1 of the first positive electrode active material layer is 100 μm to 140 μm, optionally 110 μm to 130 μm, and further optionally 115 μm to 125 μm. By controlling the thickness of the first positive electrode active material layer, it is beneficial to the improvement of the volume energy density of the secondary battery.
In one embodiment, based on the total mass of the first positive electrode active material layer, the contents of the first positive electrode active material, the first binder and the first conductive agent are 90% to 95%, 2% to 8% and 2% to 8%, respectively. By controlling the contents of the first positive electrode active material, the first binder and the first conductive agent in the first positive electrode active material layer, it is beneficial to the improvement of the volume energy density of the secondary battery.
In one embodiment, the first conductive agent and the second conductive agent are each independently selected from at least one of carbon nanotubes, conductive carbon, gas-phase carbon nanofibers, graphite, acetylene black, metal fibers, organic conductive polymers, and graphene. The first binder and the second binder are each independently selected from at least one of polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethyl cellulose and polyurethane.
A second aspect of the present application provides a secondary battery, comprising the positive electrode plate of the first aspect of the present application.
A third aspect of the present application provides a battery module, comprising the secondary battery of the second aspect of the present application.
A fourth aspect of the present application provides a battery pack, comprising the battery module of the third aspect of the present application.
A fifth aspect of the present application provides a power consuming device, comprising at least one selected from the secondary battery of the second aspect of the present application, the battery module of the third aspect of the present application or the battery pack of the fourth aspect of the present application.
The present application provides a positive electrode plate, a secondary battery, a battery module, a battery pack and a power consuming device, wherein the positive electrode plate comprises a first positive electrode active material layer and a second positive electrode active material layer, a second positive electrode active material in the second positive electrode active material layer is selected from carbon-coated LiβFeαM(1−α)PO4, an intensity ratio IA/IB of the diffraction peak A and diffraction peak B satisfies: 0.98≤IA/IB≤1.1, the proportion of crystal plane (010) of a carbon-coated lithium iron phosphate material exposed is increased, such that the active material in the second positive electrode active material layer first undergoes an electrochemical reaction and generates heat, which further promotes the active material in the first positive electrode active material layer in the secondary battery to undergo an electrochemical reaction. On this basis, in the present application, the secondary battery of the present application has a good low temperature performance by means of the synergistic effect between the first positive electrode active material layer and the second positive electrode active material layer in the positive electrode plate.
1 battery pack; 2 upper box body; 3 lower box body; 4 battery module; 5 secondary battery; 51 housing; 52 electrode assembly; 53 cover plate; 11 first positive electrode active material layer; 12 second positive electrode active material layer; 13 current collector.
Hereinafter, the embodiments of the positive electrode plate, secondary battery, battery module, battery pack and power consuming device of the present application are specifically disclosed in the detailed description with reference to the accompanying drawings as appropriate. However, unnecessary detailed illustrations may be omitted in some instances. For example, there are situations where detailed description of well known items and repeated description of actually identical structures are omitted. This is to prevent the following description from being unnecessarily verbose, and facilitates understanding by those skilled in the art. Moreover, the accompanying drawings and the descriptions below are provided for enabling those skilled in the art to fully understand the present application, rather than limiting the subject matter disclosed in claims.
“Ranges” disclosed herein are defined in the form of lower and upper limits, where a given range is defined by the selection of a lower limit and an upper limit, and the selected lower and upper limits define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if the ranges of 60-120 and 80-110 are listed for a particular parameter, it should be understood that the ranges of 60-110 and 80-120 are also contemplated. Additionally, if minimum range values 1 and 2 are listed, and maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless stated otherwise, the numerical range “a-b” denotes an abbreviated representation of any combination of real numbers between a and b, where both a and b are real numbers. For example, the numerical range “0-5” means that all real numbers between “0-5” have been listed herein, and “0-5” is just an abbreviated representation of combinations of these numerical values. In addition, when a parameter is expressed as an integer of ≥2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the like.
All the implementations and optional implementations of the present application can be combined with one another to form new technical solutions, unless otherwise stated.
All technical features and optional technical features of the present application can be combined with one another to form a new technical solution, unless otherwise stated.
Unless otherwise stated, all the steps of the present application can be performed sequentially or randomly, preferably sequentially. For example, the method including steps (a) and (b) indicates that the method may include steps (a) and (b) performed sequentially, and may also include steps (b) and (a) performed sequentially. For example, reference to “the method may further include step (c)” indicates that step (c) may be added to the method in any order, e.g., the method may include steps (a), (b) and (c), steps (a), (c) and (b), and also steps (c), (a) and (b), etc.
The terms “comprise” and “include” mentioned in the present application are open-ended or closed-ended, unless otherwise stated. For example, “comprise” and “include” may mean that other components not listed may further be comprised or included, or only the listed components may be comprised or included.
In the present application, the term “or” is inclusive unless otherwise specified. For example, the phrase “A or B” means “A, B, or both A and B”. More specifically, a condition “A or B” is satisfied by any one of the following: A is true (or present) and B is false (or not present); A is false (or not present) and B is true (or present); or both A and B are true (or present).
In the specific embodiments of the present application, the present application is explained by means of using a lithium-ion battery as an example of secondary batteries, but the secondary batteries in the present application are not limited to lithium-ion batteries.
During the research of lithium iron phosphate material batteries, the inventors of the present application found that lithium iron phosphate materials have the problem of poor low-temperature conductivity, which makes it difficult for the capacity and working voltage of lithium iron phosphate batteries to meet application requirements at low temperatures, thus affecting the low temperature performance of lithium iron phosphate material batteries. In order to improve the low temperature performance of lithium iron phosphate material batteries such that the lithium iron phosphate material batteries have better performance such as a longer range and a longer life at a low temperature when used in a power consuming device, in view of this, the present application provides a positive electrode plate, a secondary battery, a battery module, a battery pack and a power consuming device.
In one embodiment of the present application, the present application proposes a positive electrode plate, as an example, as shown in
The first positive electrode active material layer comprises a first positive electrode active material, a first binder and a first conductive agent, wherein the first positive electrode active material is selected from at least one of LiqCoO2, Li1+xCo1−y−zNiyMnzO2 or carbon-coated LiβFeαM(1−α)PO4, wherein 0≤q≤1, 0≤x≤0.1, 0≤y≤0.95, 0≤z≤0.95, 0.2≤α≤1, 1≤β≤1.1, and M is selected from at least one of Cu, Mn, Cr, Zn, Pb, Ca, Co, Ni and Sr; and the second positive electrode active material layer comprises a second positive electrode active material, a second binder and a second conductive agent, wherein the second positive electrode active material is selected from carbon-coated LiβFeαM(1−α)PO4, where 0.2≤α≤1, 1≤β≤1.1, M is selected from at least one of Cu, Mn, Cr, Zn, Pb, Ca, Co, Ni, and Sr, and the second positive electrode active material has a diffraction peak A between 29° and 30° in the X-ray diffraction pattern, and a diffraction peak B between 25° and 26°, and the intensity ratio IA/IB of the diffraction peaks satisfies: 0.98≤IA/IB≤1.1, optionally 1.05≤IA/IB≤1.1.
Although the mechanism is not yet clear, the inventor of the present application has unexpectedly discovered: a second positive electrode active material in the second positive electrode active material layer is selected from carbon-coated LiβFeαM(1-α)PO4; by controlling an intensity ratio of the diffraction peaks in the X-ray diffraction pattern of the second positive electrode active material, the proportion of crystal plane (010) of the carbon-coated lithium iron phosphate material (such as carbon-coated LiβFeαM(1−α)PO4) exposed is increased, such that the active material in the second positive electrode active material layer first undergoes an electrochemical reaction and generates heat, which further promotes the active material in the first positive electrode active material layer in the lithium ion battery to further undergo an electrochemical reaction, and by means of the synergistic effect between the first positive electrode active material layer and the second positive electrode active material layer in the positive electrode plate, the capacity retention rate and power performance of the lithium ion battery under low temperature conditions can be effectively improved, thus the overall low temperature performance of the secondary battery can be improved.
The inventor of the present application has found that the second positive electrode active material has a diffraction peak A between 29° and 30° in the X-ray diffraction pattern, and a diffraction peak B between 25° and 26°, wherein the higher intensity ratio of diffraction peaks IA/IB results in a higher proportion of crystal plane (010) of the carbon-coated lithium iron phosphate material (such as carbon-coated LiβFeαM(1−α)PO4) exposed. It is speculated that this may be due to the intercalation and deintercalation of lithium ions in the carbon-coated lithium iron phosphate material along the b-axis during the electrochemical reaction. Therefore, the higher the exposure ratio of (010) crystal plane, the better the electrochemical reaction kinetics. Therefore, the second positive electrode active material having the diffraction peak intensity ratio of the present application exhibits excellent low temperature performance when applied to a lithium ion battery. The inventor of the present application also found that when the intensity ratio IA/IB of the diffraction peaks satisfies: 1.05≤IA/IB≤1.1, the low temperature performance of a secondary battery prepared by the above materials is further improved.
On this basis, when the lithium ion battery prepared by the above positive electrode plate is charged and discharged at a low temperature, the active material in the second positive electrode active material layer of the positive electrode plate first undergoes an electrochemical reaction and generates heat, which further promotes the active material in the first positive electrode active material layer in the lithium ion battery to further undergo an electrochemical reaction, and by means of the synergistic effect between the first positive electrode active material layer and the second positive electrode active material layer, the overall low temperature performance of the secondary battery is improved.
In some embodiments, the thickness D2 of the second positive electrode active material layer in the positive electrode plate of the present application is 2 μm to 40 μm, optionally 10 μm to 30 μm, and further optionally 15 μm to 25 μm. By making the thickness of the second positive electrode active material layer within the above range, the following situations can be avoided: the thickness of the second positive electrode active material layer is too large, which may affect the volume energy density of the lithium ion battery, and the thickness of the second positive electrode active material layer is too small, which may affect the low temperature performance of the lithium ion battery. Therefore, in the present application, by controlling the thickness of the second positive electrode active material layer within the above range, it is beneficial to balance the low temperature performance and volume energy density of the lithium ion battery.
In some embodiments, the average particle size of the primary particles of the second active material of the present application is 20 nm to 240 nm, optionally 20 nm to 160 nm, and further optionally 20 nm to 80 nm. The inventor of the present application found that when the particle size of the primary particles of the second active material is within the above range, the diffusion path of lithium ions during the electrochemical reaction can be shortened, and a shorter transmission channel for lithium ions can be provided, such that the secondary battery, under a low temperature or high rate discharge, has smaller battery polarization, and lower voltage drop, and the good discharge capacity is maintained, thereby improving the low temperature performance of the secondary battery.
In some embodiments, based on the total mass of the second positive electrode active material layer, the contents of the second positive electrode active material, the second binder and the second conductive agent are 80% to 98%, 1% to 10% and 1% to 10%, respectively. Without being limited to any theory, by controlling the contents of the positive electrode active material, the binder and the conductive agent in the second positive electrode active material layer with in the above range, the capacity retention rate and power performance of the secondary battery under low temperature conditions can be improved.
In some embodiments, the thickness D1 of the first positive electrode active material layer is 100 μm to 140 μm, optionally 110 μm to 130 μm, and further optionally 115 μm to 125 μm. Without being limited to any theory, by controlling the thickness of the first positive electrode active material layer within the above range, it is beneficial to the improvement of the volume energy density of the secondary battery.
In some embodiments, based on the total mass of the first positive electrode active material layer, the contents of the first positive electrode active material, the first binder and the first conductive agent are 90% to 95%, 2% to 8% and 2% to 8%, respectively. Without being limited to any theory, by controlling the contents of the positive electrode active material, the binder and the conductive agent in the first positive electrode active material layer within the above range, it is beneficial to the improvement of the volume energy density of the secondary battery.
The first conductive agent and the second conductive agent are not particularly limited in the present application as long as the objectives of the present application can be achieved. In some embodiments, the first conductive agent and the second conductive agent are each independently selected from at least one of carbon nanotubes, conductive carbon, gas-phase carbon nanofibers, graphite, acetylene black, metal fibers, organic conductive polymers, and graphene.
The first binder and the second binder are not particularly limited in the present application as long as the objectives of the present application can be achieved. In some embodiments, the first binder and the second binder are each independently selected from at least one of polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethyl cellulose and polyurethane.
The average particle size of the primary particles of the first active material is not particularly limited in the present application, e.g. 800 nm to 3000 nm, as long as the objectives of the present application can be achieved.
The position of the first positive electrode active material layer and the second positive electrode active material layer above and below the current collector are not particularly limited in the present application as long as the objectives of the present application can be achieved. In some embodiments, referring to
The coating method of the first positive electrode active material layer and the second positive electrode active material layer is not particularly limited in the present application as long as the objectives of the present application can be achieved. In some embodiments, the first positive electrode active material layer and the second positive electrode active material layer may be sequentially coated. In some embodiments, the first positive electrode active material layer and the second positive electrode active material layer may be coated simultaneously.
The preparation method of the carbon-coated LiβFeαM(1-α)PO4 active material in the second positive electrode active material layer is not particularly limited in the present application as long as the objectives of the present application can be achieved. In some embodiments, it can be prepared by liquid phase synthesis, comprising the following steps:
step A: mixing an iron source, a lithium source and a phosphorus source according to a certain ratio (for example, the iron source, lithium source and phosphorus source are mixed according to the ratio of iron, phosphorus and lithium atom concentration of 0.5 mol:0.65 mol:1.5 mol), adding a solvent and mixing same to obtain a mixed solution A, wherein the solvent is selected from an alcohol, water or a mixture of an alcohol and water, and the alcohol is selected from at least one of ethanol, methanol, ethylene glycol and glycerol; the iron source is selected from at least one of ferrous sulfate, ferrous chloride and ferrous acetate; the phosphorus source is selected from at least one of phosphoric acid and ammonium dihydrogen phosphate; and lithium hydroxide can be used as the lithium source;
step B: after adding a surfactant (for example, the mass ratio of the surfactant to the mixed solution A is 1:100) to the mixed solution A, adding a pH modifier to adjust the pH of the mixed solution A to 7-8 to obtain a mixed solution B, wherein the surfactant is selected from one of sodium citrate, sodium lactate, sodium malate and sodium tartrate;
step C: transferring the mixed solution B to a reaction kettle, sealing same at a temperature of 170° C. to 250° C. and reacting same for 1 h to 6 h, after cooling, filtering and washing the precipitate obtained by the reaction to obtain a lithium iron phosphate material;
the inventor of the present application found that during the hydrothermal precipitation of lithium iron phosphate, the (010) crystal plane exposes more iron ions, and due to the coordination effect, the surfactant is adsorbed on the (010) crystal plane, limiting the further growth rate of the (010) crystal plane, such that the thickness in the [010] crystallographic direction decreases, and the energy required for the deintercalation reaction of lithium ions along the [010] crystallographic direction is the lowest, which can significantly improve the transmission speed of lithium ions and reduce the solid-phase reaction diffusion resistance; and
step D: after drying, uniformly mixing the obtained lithium iron phosphate material with a carbon source (the mass ratio of lithium iron phosphate material to the carbon source is 20:1), and then sintering and carbonizing same in an inert nitrogen atmosphere to obtain a carbon-coated LiβFeαM(1-α)PO4 active material, wherein the carbon source can be selected from at least one of glucose, sucrose, starch and polyethylene glycol, and the carbonization temperature is 750° C. to 800° C.
In the present application, the intensity ratio IA/IB of the diffraction peaks can be regulated by controlling parameters such as the reaction time t in the liquid phase method, the concentration C of the reactant, the concentration Cx of the surfactant added, or the selected type of the surfactant. The inventor of the present application found that the IA/IB value is increasing with the prolongation of the reaction time, but when the reaction time continues to prolong, the IA/IB value would show a downward trend. At the initial stage of the reaction, the lithium iron phosphate nanoparticles grow directionally under the control of the surfactant, and with the increase of the crystal volume, the increase of IA dominates; but when the reaction time is too long, the epitaxial growth of the (010) crystal plane will reach a equilibrium. The increase in nanoparticle thickness values parallel to the [010] crystallographic orientation leads to a decrease in the proportion of (010) crystal plane exposed. Based on this, in the present application, the liquid-phase reaction time is regulated to be 1 h to 6 h, and within this reaction time range, the IA/IB value increases with the prolongation of the reaction time.
The lower concentration of reactant is beneficial to the increase of IA/IB value, but too low concentration of reactant will prolong the reaction end time and lower the production efficiency. The mass ratio of the surfactant to the mixed solution A can be controlled within the range of 1:100 to 1000.
The preparation method of the carbon-coated LiβFeαM(1-α)PO4 active material in the first positive electrode active material layer is not particularly limited in the present application as long as the objectives of the present application can be achieved. In some embodiments, common solid-phase methods or hydrothermal synthesis methods may be employed. Of course, in the present application, the carbon-coated LiβFeαM(1-α)PO4 active material in the first positive electrode active material layer can also be prepared by a liquid phase synthesis method.
In the present application, the carbon-coated LiβFeαM(1-α)PO4 active material prepared by the liquid phase synthesis method has a nanoscale size, and the following formula can be obtained by Fick's first law:
wherein Id is the limiting diffusion current density, n is the number of moles of charge transferred during the electrochemical reaction, F is the Faraday constant, Ci is the surface carrier concentration under complete concentration polarization, and l is the path length of the carrier diffusion from the inside of the nanomaterial to the external interface.
During the charging and discharging of lithium-ion batteries, the nanomaterials with larger Id will show better low-temperature performance and power performance. For the carbon-coated lithium iron phosphate nanomaterial prepared by the liquid phase synthesis method, the diffusion path of lithium ions in the electrochemical reaction is shortened, which makes the carbon-coated lithium iron phosphate material prepared by the method show a high limiting diffusion current density, such that the lithium-ion battery has a good low temperature performance. The carbon-coated lithium iron phosphate material synthesized by a conventional method (such as a solid phase method), as shown in
The secondary battery, battery module, battery pack, and power consuming device of the present application will be described below by appropriately referring to the accompanying drawings.
In an embodiment of the present application, a secondary battery is provided, comprising the positive electrode plate according to any one of the above embodiments. The secondary battery of the present application may refer to the lithium-ion battery according to any one of the above embodiments.
Typically, a secondary battery comprises a positive electrode plate, a negative electrode plate, an electrolyte and a separator. During the charge/discharge process of the battery, active ions are intercalated and de-intercalated back and forth between the positive electrode plate and the negative electrode plate. The electrolyte is located between the positive electrode plate and the negative electrode plate and functions for ionic conduction. The separator is provided between the positive electrode plate and the negative electrode plate, and mainly prevents the positive and negative electrodes from short-circuiting and enables ions to pass through.
[Negative Electrode Plate]
In some embodiments, the negative electrode current collector of the negative electrode plate may be a metal foil or a composite current collector. For example, as a metal foil, a copper foil can be used. The composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by forming a metal material (copper, a copper alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver and a silver alloy, etc.) on a polymer material substrate (e.g., polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the negative electrode plate can be prepared as follows: a first negative electrode slurry and a second negative electrode slurry are prepared; the second negative electrode slurry is coated on the current collector to form a second coating, and then the first negative electrode slurry is coated on a surface of the second coating to form a first coating; or a double-sided coating device may also be used in the coating to coat the first negative electrode slurry and the second negative electrode slurry on the current collector simultaneously; and procedures such as drying and cold pressing are performed to obtain a negative electrode plate, in which the current collector is on one side of the second coating, and the first coating is on the other side of the second coating.
[Electrolyte]
The electrolyte is located between the positive electrode plate and the negative electrode plate and functions for ionic conduction. The type of the electrolyte is not specifically limited in the present application, and can be selected according to actual requirements. For example, the electrolyte may be liquid, gel or all solid.
In some embodiments, an electrolyte solution is used as the electrolyte. The electrolyte solution comprises an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium dioxalate borate, lithium difluorodioxalate phosphate and lithium tetrafluorooxalate phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, sulfolane, dimethyl sulfone, ethyl methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte solution may optionally comprise an additive. For example, the additive can include a negative electrode film-forming additive, a positive electrode film-forming additive, and also an additive that can improve certain performances of the battery, such as an additive that improve the overcharge performance of the battery, or an additive that improve the high temperature performance or low-temperature performance of the battery.
[Separator]
In some embodiments, the secondary battery further comprises a separator. The type of the separator is not particularly limited in the present application, and any well known porous-structure separator with good chemical stability and mechanical stability may be selected.
In some embodiments, the material of the separator can be selected from at least one of glass fibers, a non-woven, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film and also a multi-layer composite film, and is not limited particularly. When the separator is a multi-layer composite film, the materials in the respective layers may be same or different, which is not limited particularly.
In some embodiments, an electrode assembly may be formed by a positive electrode plate, a negative electrode plate and a separator by a winding process or a laminating process.
In some embodiments, the secondary battery may comprise an outer package. The outer package can be used to encapsulate the above-mentioned electrode assembly and electrolyte.
In some embodiments, the outer package of the secondary battery can be a hard shell, for example, a hard plastic shell, an aluminum shell, a steel shell, etc. The outer package of the secondary battery may also be a soft bag, such as a pouch-type soft bag. The material of the soft bag may be plastics, and the examples of plastics may include polypropylene, polybutylene terephthalate, and polybutylene succinate, etc.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square or of any other shape. For example,
In some embodiments, referring to
In some embodiments, the secondary battery can be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
Optionally, the battery module 4 may also comprise a housing with an accommodating space, and a plurality of secondary batteries 5 are accommodated in the accommodating space.
In some embodiments, the above-mentioned battery module may also be assembled into a battery pack, the number of battery modules included in the battery pack may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
In addition, the present application further provides a power consuming device. The power consuming device comprises at least one of the secondary battery, battery module, or battery pack provided by the present application. The secondary battery, battery module or battery pack may be used as a power source of the power consuming device or as an energy storage unit of the power consuming device. The power consuming device may include a mobile device (e.g., a mobile phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck), an electric train, ship, and satellite, an energy storage system, and the like, but is not limited thereto.
As for the power consuming device, the secondary battery, battery module or battery pack can be selected according to the usage requirements thereof.
As another example, the device may be a mobile phone, a tablet, a laptop computer, etc. The device is generally required to be thin and light, and may use a secondary battery as a power source.
Hereinafter, the examples of the present application will be explained. The examples described below are exemplary and are merely for explaining the present application, and should not be construed as limiting the present application. The techniques or conditions that are not specified in examples are according to the techniques or conditions described in documents in the art or the product introduction. The reagents or instruments used, if they are not marked with the manufacturer, are common products that are commercially available.
<Preparation of Positive Electrode Plate>
<Preparation of First Positive Electrode Slurry>
The carbon-coated LiFePO4 with a primary particle average particle size of 800 nm as a first positive electrode active material (obtained by a solid-phase method), a binder polyvinylidene fluoride (PVDF), and a conductive carbon acetylene black are dry-mixed according to the weight ratio of 95:3:2, then N-methylpyrrolidone (NMP) is added as a solvent, and the system is stirred under the action of a vacuum mixer until the system is homogeneous to obtain a first positive electrode slurry with a viscosity of 20000 mPa·s.
<Preparation of Second Positive Electrode Slurry>
The carbon-coated LiFePO4 with a primary particle average particle size of 80 nm as a second positive electrode active material (obtained by a liquid-phase method), a binder polyvinylidene fluoride (PVDF), and a conductive carbon acetylene black are dry-mixed according to the weight ratio of 95:3:2, then N-methylpyrrolidone (NMP) is added as a solvent, and the system is stirred under the action of a vacuum mixer until the system is homogeneous to obtain a second positive electrode slurry with a viscosity of 20000 mPa·s.
<Preparation of Positive Electrode Plate Containing First Active Material Layer and Second Active Material Layer>
The prepared second positive electrode slurry is uniformly coated onto the surface of the current collector aluminum foil with a thickness of 12 μm at a coating weight of 20 g/m2, and dried in an oven at 100° C. to obtain a second active material layer with a thickness of 8.5 μm. The first positive electrode slurry is uniformly coated onto the surface of the second active material layer with a coating weight of 260 g/m2, and dried in an oven at 100° C. to obtain a first active material layer with a thickness of 110 μm, forming a structure as shown in
<Preparation of Negative Electrode Plate>
1) a negative electrode active material graphite, a conductive agent conductive carbon black and a binder butadiene styrene rubber and sodium carboxymethylcellulose are mixed in a mass ratio of 93:3:2:2, deionized water is added as a solvent, and the system is stirred under the action of a vacuum mixer until the system is homogeneous, to obtain a negative electrode slurry with a viscosity of 20000 mPa·s, and
2) the prepared negative electrode slurry is uniformly coated onto the surface of a copper foil with a thickness of 8 μm at a coating weight of 200 g/m2, and dried in an oven at 100° C. following by processes such as cold pressing, tab forming, and slitting to obtain a negative electrode plate.
<Preparation of Electrolyte Solution>
In an environment with a water content of less than 10 ppm, non-aqueous organic solvents ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were mixed in a volume ratio of 1:1:1 to obtain an electrolyte solution solvent, and then a lithium salt LiPF6 was dissolved in the mixed solvent, to make an electrolyte solution with a lithium salt concentration of 1 mol/L.
<Preparation of Separator>
A polyethylene film with a thickness of 9 μm was selected as a separator, and before use, the separator was slitted to obtain a suitable width according to the dimensions of the positive electrode plate and the negative electrode plate.
<Preparation of Lithium-Ion Battery>
The above positive electrode plate, a separator and negative electrode plate are punched into a plate, such that the separator was located between the positive electrode plate and the negative electrode plate to play a role of isolation, and then the plate is stacked several times to obtain an electrode assembly; and the electrode assembly was placed in an outer package and dried, and then an electrolyte solution was injected, followed by the procedures such as vacuum encapsulation, standing, forming and shaping, to obtain a lithium-ion battery.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 1, except that the reaction time of the liquid phase synthesis process is adjusted to change the diffraction peak intensity ratio IA/IB value of the second active material in the X-ray pattern as shown in Table 1.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 1, except that the average particle size of the primary particles of the second active material is adjusted as shown in Table 1.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 1, except that the thickness of the second positive electrode active material layer and the coating weight of the first positive electrode active material are adjusted as shown in Table 1.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 1, except that the type of the second positive electrode active material is adjusted as shown in Table 1.
The procedure is the same as that of Example 6, except that in <Preparation of positive electrode plate containing first positive electrode active material layer and second positive electrode active material layer>, the first positive electrode slurry is first coated onto the current collector to obtain the first positive electrode active material layer, and then the second positive electrode slurry is coated onto the surface of the first positive electrode active material layer to form the structure shown in
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 1, except that the type of the first positive electrode active material and the thickness of the first positive electrode active material layer are adjusted as shown in Table 1.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 6, except that the diffraction peak intensity ratio in the X-ray pattern of the second active material is adjusted as shown in Table 1.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 1, except that the average particle size of the primary particles of the second active material is adjusted as shown in Table 1.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 8, except that the thickness of the second positive electrode active material layer and the coating weight of the first positive electrode active material are adjusted as shown in Table 1.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 1, except that the second positive electrode active material layer is not prepared.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 17, except that the second positive electrode active material layer is not prepared.
In the <Preparation of positive electrode plate>, the procedure is the same as that of Example 18, except that the second positive electrode active material layer is not prepared.
A/
B
indicates data missing or illegible when filed
A/ B
5
5PO4
4Mn0
PO4
2Ni0
5
3O2
5Co0
2
3O2
indicates data missing or illegible when filed
In addition, the secondary batteries prepared in the above-mentioned Examples 1 to 18 and comparative examples 1 to 8 are tested for performance, and the test results are shown in Table 3 and Table 4 below.
Capacity Retention Rate Test at −20° C.:
After the lithium-ion batteries prepared in each example and comparative example are kept at 25° C. for 2 h, they are charged to 3.65 V with a constant current rate of 0.33 C, and charged to 0.05 C with a constant voltage at 3.65 V. After the charging is completed, the tested battery is allowed to stand at 25° C. for 2 h, and then discharged to 2.5 V at a rate of 0.5 C by means of a direct current, and the discharge capacity at room temperature thereof is recorded as C0.
After the lithium-ion batteries prepared in each example and comparative example are kept at 25° C. for 2 h, they are charged to 3.65 V with a constant current rate of 0.33 C, and charged to 0.05 C with a constant voltage at 3.65 V. After the charging is completed, the tested battery is allowed to stand at −20° C. for 2 h, and then discharged to 2.5 V at a rate of 0.5 C by means of a direct current, and the discharge capacity at −20° C. thereof is recorded as C1. The capacity retention rate of the lithium-ion battery at −20° C. is: (C1/Co)×100%.
Power Performance Test at −20° C.:
Capacity calibration: After the lithium-ion batteries prepared in each example and comparative example are kept at 25° C. for 2 h, they are charged to 3.65 V with a constant current rate of 0.33 C, and charged to 0.05 C with a constant voltage at 3.65 V. After the charging is completed, the tested battery is allowed to stand at 25° C. for 2 h, and then discharged to 2.5 V at a rate of 0.33 C by means of a direct current, and the discharge capacity at room temperature thereof is recorded as C0.
Adjustment of SOC (state of charge): After the lithium-ion battery with the calibrated capacity is kept at 25° C. for 2 h, it is discharged at a discharge rate of 1/3 C0 for 144 min, and the capacity of the lithium-ion battery is adjusted to 20% SOC;
Power test: the lithium-ion battery of 20% SOC is allowed to stand at −20° C. for 2 h, then under a pulse current I, is discharged at a discharge rate of 3 Co for 30 s, the voltage thereof before 3 C0 discharge is recorded as V1, and the voltage at the end of 30 s discharge is recorded as V2; The value of (V1−V2)/I is calculated, through which the power performance of the battery can be characterized.
Calculation of Volume Energy Density Ex at −20° C.:
After the lithium-ion batteries prepared in each example and comparative example are kept at 25° C. for 2 h, they are charged to 3.65 V with a constant current rate of 0.33 C, and charged to 0.05 C with a constant voltage at 3.65 V. After the charging is completed, the tested battery is allowed to stand at −20° C. for 2 h, and then discharged to 2.5 V at a rate of 0.33 C by means of a direct current, the discharge energy E0 (wh) of the lithium battery thereof, the coating area S (dm2) of the positive electrode plate and the thickness h (dm) of the positive electrode plate are recorded, then the volume energy density Ex=E0/(S×h).
Diffraction Peak Intensity Ratio Test:
The diffraction peak intensity ratio of the second positive electrode active material is tested by X-ray, wherein a copper target X-ray diffractometer is used, the second active material is placed on the X-ray diffractometer (model Shimadzu XRD-7000) test platform, the start angle of scan is 10°, the end angle is 90°, and a step size is 0.013, and then the test is started to obtain the diffraction pattern of the second active material in the range of the diffraction angle of 10° to 90°, and the diffraction peak intensity ratio IA/IB is determined according to the diffraction pattern.
According to the above results, it can be seen that in example 1 to example 18, by controlling the intensity ratio IA/IB of the diffraction peak A to the diffraction peak B of the second positive electrode active material in the second positive electrode active material layer to satisfy: 0.98≤IA/IB≤1.1, a lithium ion battery with good low temperature performance as a whole can be obtained.
From example 1 to example 4 and comparative example 1 to comparative example 2, it can be seen that the positive electrode plate of the lithium ion battery includes a first positive electrode active material layer and a second positive electrode active material layer, wherein the intensity ratio IA/IB of the diffraction peak A to the diffraction peak B of the second positive electrode active material in the second positive electrode active material layer satisfies: 0.98≤IA/IB≤1.1, such that the lithium ion battery has good low temperature capacity retention rate, low temperature power performance and low temperature volume energy density, and has achieved good results. In contrast, the lithium ion batteries of comparative examples 1 to 2 do not achieve effective improvement in the low temperature capacity retention rate, low temperature power performance and low temperature volume energy density due to the fact that the diffraction peak intensity ratio IA/IB is too low or too high. That is, the low temperature performance has not been effectively improved.
From example 1, it can also be seen that the low temperature performance of the lithium ion battery with the second positive electrode active material layer of the present application is improved. In contrast, the lithium ion battery of comparative example 6 does not have the second positive electrode active material layer and does not achieve the effective improvement in the low temperature capacity retention rate, low temperature power performance and low temperature volume energy density. That is, the low temperature performance has not been effectively improved.
From example 1, example 5 to example 7 and comparative example 3, it can be seen that if the average particle size of the primary particles of the second positive electrode active material is too large, the lithium ion transmission path increases, and the excessively long lithium ion transmission path is not conducive to an electrochemical reaction, so that the ability of the second positive electrode active material layer to improve the low temperature performance is greatly inhibited, and if the average particle size of the primary particles of the second positive electrode active material is too small, the compaction density of the second positive electrode active material layer will decrease, which is not conducive to the improvement of the lithium ion energy density. By adjusting and controlling the average particle size of the primary particles of the second positive electrode active material to be within the range of the present application, a lithium ion battery with good low temperature performance can be obtained.
From example 8 to example 13 and comparative example 4 to comparative example 5, it can be seen that when the thickness of the second positive electrode active material layer is too low (for example, comparative example 4), the low temperature performance of the lithium ion battery cannot be significantly improved; and when the thickness of the second positive electrode active material layer is too high (for example, comparative example 5), the volume energy density of the lithium ion battery decreases. By adjusting and controlling the average particle size of the primary particles of the second positive electrode active material to be within the range of the present application, a lithium ion battery with good low temperature performance and volume energy density can be obtained.
The thickness of the second positive electrode active material layer, the type of the second positive electrode active material, and the type of the first positive electrode active material will also affect the low temperature performance of the lithium ion battery of the present application. It can be seen from Examples 5 to 18 that, as long as the above parameters are within the scope of the present application, a lithium ion battery with good comprehensive low temperature performance can be obtained.
It can be seen from Example 6 and Example 16 that the first positive electrode active material layer is arranged between the current collector and the second positive electrode active material layer, or the second positive electrode active material layer is arranged between the current collector and the first positive electrode active material layer, the low temperature performance of the lithium ion battery can be effectively improved.
From examples 17 and 18, it can be seen that for the lithium ion battery with the second positive electrode active material layer of the present application, the capacity retention rate at −20° C. and the low temperature performance thereof are improved. In contrast, the lithium ion batteries of comparative examples 7 and 8 do not have the second positive electrode active material layer and does not achieve the effective improvement in the capacity retention rate at −20° C.
It should be noted that the present application is not limited to the above embodiments. The above embodiments are exemplary only, and any embodiment that has substantially same constitutions as the technical ideas and has the same effects within the scope of the technical solution of the present application falls within the technical scope of the present application. In addition, without departing from the gist of the present application, various modifications that can be conceived by those skilled in the art to the embodiments, and other modes constructed by combining some of the constituent elements of the embodiments also fall within the scope of the present application.
The present application is a continuation of International Application No. PCT/CN2021/134449, filed Nov. 30, 2021, which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2021/134449 | Nov 2021 | US |
| Child | 18084551 | US |
