Patent Application
20250125488
The present application belongs to the field of battery technology, and in particular relates to a separator, a method for preparing the same, and a secondary battery and an electrical device related thereto.
In recent years, secondary batteries have been widely used in energy storage power systems such as hydraulic, thermal, wind and solar power plants, as well as in many fields such as electric tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, and aerospace. With the application and promotion of secondary batteries, their service life and safety issues, especially thermal safety issues, have received more and more attention. However, the existing methods for improving the thermal safety performance of secondary batteries are often not conducive to balancing the energy density of secondary batteries. Therefore, how to obtain a secondary battery having the combined characteristics of high energy density, high thermal safety performance and long service life is a key challenge in designing secondary battery.
An object of the present application is to provide a separator, a method for preparing the same and a secondary battery and an electrical device related thereto, wherein the separator has the characteristics including excellent heat resistance, low moisture content and good electrolyte infiltration, so that a secondary battery using the separator can have the combined characteristics of high energy density, high thermal safety performance, and long service life.
A first aspect of the present application provides a separator, comprising a porous substrate and a coating layer disposed on one or more surface of the porous substrate, wherein the coating layer comprises nanocellulose and a filler, and the separator has a moisture content of A ppm, the coating layer has a thickness of H μm, and the separator satisfies 250≤A/H≤1500.
The inventors of the present application have unexpectedly found, through a lot of research, that by disposing a coating layer comprising nanocellulose and a filler on one or more surface of the porous substrate of the separator and controlling the ratio of the moisture content of the separator to the thickness of the coating layer within the above-mentioned specific range, the separator can have the combined characteristics of high heat resistance, low moisture content and good electrolyte infiltration.
In some embodiments of the present application, 500≤A/H≤1500, optionally, 600≤A/H≤1000. As a result, this facilitates the coating layer having more stable spatial network structure and more suitable content of hydroxyl functional groups, so that the separator can have the combined characteristics of high heat resistance, low moisture content and good electrolyte infiltration, and the secondary battery can have the combined characteristics of high thermal safety performance, long cycle life and long storage life.
In some embodiments of the present application, 400≤A≤1000, optionally, 500≤A≤800. As a result, this facilitates the coating layer having more stable spatial network structure and more suitable content of hydroxyl functional groups, so that the separator can better have combined characteristics of high heat resistance, low moisture content and good electrolyte infiltration and can further improve the cycle life and storage life of the secondary battery.
In some embodiments of the present application, 0<H≤1.5, optionally, 0.2≤H≤0.8. As a result, this contributes to improving the energy density of the secondary battery.
In some embodiments of the present application, the nanocellulose comprises one or more of cellulose nanofibers, cellulose nanowhiskers and bacterial nanocellulose, and is optionally cellulose nanowhiskers. The cellulose nanowhiskers may have higher crystallinity, thereby reducing their hydrophilicity, which in turn facilitates moisture discharge during the drying process and thus results in lower moisture content in the separator of the present application.
In some embodiments of the present application, the nanocellulose comprises one or more of unmodified nanocellulose and modified nanocellulose, and optionally is modified nanocellulose.
In some embodiments of the present application, the modified nanocellulose comprises a modifying group, and the modifying group comprises one or more of an amino group, a carboxylic acid group, an aldehyde group, a sulfonic acid group, a boric acid group, and a phosphoric acid group, and optionally comprises one or more of a sulfonic acid group, a boric acid group, and a phosphoric acid group. When the nanocellulose has the above-mentioned specific modifying groups, on one hand, the modifying groups can effectively improve the heat resistance of the separator and improve the thermal safety performance of the secondary battery; on another hand, the modifying groups further facilitates a separator having a lower moisture content under the premise of good electrolyte infiltration, thereby further improving the electrochemical performance of the secondary battery.
In some embodiments of the present application, the modified nanocellulose comprises a hydroxyl group and a modifying group, and a molar ratio of the modifying group to the hydroxyl group is from 1:4 to 4:1, optionally from 2:3 to 7:3. When the molar ratio of the modifying group to the hydroxyl group is in the appropriate ranges, the heat resistance and ion transport properties of the separator may be further improved, and the separator has a lower moisture content.
In some embodiments of the present application, the nanocellulose has an aspect ratio of from 5 to 80, optionally from 10 to 40. When the aspect ratio of the nanocellulose is in the appropriate ranges, the heat resistance and ion transport properties of the separator may be further improved.
In some embodiments of the present application, the nanocellulose has an average diameter of from 10 nm to 40 nm, optionally from 10 nm to 35 nm. When the average diameter of the nanocellulose is within the appropriate ranges, the heat resistance, ion transport property and voltage breakdown resistance property of the separator may be further improved.
In some embodiments of the present application, the nanocellulose has an average length of from 100 nm to 600 nm, optionally from 200 nm to 500 nm. When the average length of the nanocellulose is in the appropriate ranges, the heat resistance and ion transport properties of the separator may be further improved.
In some embodiments of the present application, the nanocellulose has a weight average molecular weight of from 10000 to 60000, optionally from 30000 to 50000.
In some embodiments of the present application, the nanocellulose has an equilibrium degree of polymerization of from 150 DP to 300 DP, optionally from 200 DP to 250 DP.
When the weight average molecular weight and/or degree of polymerization of nanocellulose is/are in the appropriate ranges, not only nanocellulose may be prevented from blocking the pore/channel structure of the separator, but also the viscosity of the coating slurry may be in an appropriate range. As a result, the slurry may have better fluidity and infiltration during coating, which is more conducive to improving the quality of the coating layer.
In some embodiments of the present application, the nanocellulose in the coating layer is present in an amount of from 6 wt. % to 35 wt. %, optionally from 10 wt. % to 30 wt. %, based on the total weight of the coating layer.
In some embodiments of the present application, the filler in the coating layer is present in an amount of ≥60 wt. %, optionally from 65 wt. % to 90 wt. %, based on the total weight of the coating layer.
When the amount of nanocellulose and/or the amount of filler is/are in the appropriate ranges, it can ensure that the coating slurry has an appropriate viscosity, which is more conducive to coating process, and is also conducive to the lower moisture content and good electrolyte infiltration of the separator; in addition, it is also conducive to the formation of a stable spatial network structure from the filler and nanocellulose.
In some embodiments of the present application, the filler comprises one or more selected from inorganic particles and organic particles.
In some embodiments of the present application, the filler has a decomposition temperature of 200° C. or higher.
In some embodiments of the present application, the filler comprises a first filler, and the first filler is of secondary particle morphology formed by agglomeration of primary particles. As a result, the nanocellulose can also make contact in the gap between the primary particles for forming the filler with secondary particle morphology, so that the nanocellulose and the first filler make contact to form an integrated effect, and the resulting coating layer may have a more stable spatial network structure and thus the separator may have a suitable porosity and a stable pore/channel structure, meanwhile the separator may have the combined characteristics of low moisture content and good electrolyte infiltration.
In some embodiments of the present application, the first filler is present in an amount of from 50 wt. % to 100 wt. %, optionally from 90 wt. % to 99 wt. %, based on the total weight of the filler.
In some embodiments of the present application, the first filler has an average particle size Dv50 of ≤200 nm, optionally from 50 nm to 200 nm.
In some embodiments of the present application, the first filler has a BET specific surface area of ≥20 m2/g, optionally from 25 m2/g to 50 m2/g.
When one or more of the amount, the average particle size Dv50 and the BET specific surface area of the first filler is within the above ranges, the first filler can make contact with the nanocellulose to form an integrated effect, and the resulting coating layer may have a more stable spatial network structure, meanwhile the separator may have better heat resistance and electrolyte infiltration.
In some embodiments of the present application, the first filler comprises inorganic particles with secondary particle morphology, and the inorganic particles with secondary particle morphology have a crystal form including at least two of α crystal form, θ crystal form, γ crystal form and η crystal form, optionally have a crystal form including at least two of α crystal form, θ crystal form, and γ crystal form.
In some embodiments of the present application, the first filler comprises inorganic particles with secondary particle morphology, and the inorganic particles with secondary particle morphology have a crystal form including θ crystal form, and the θ crystal form is present in an amount of ≥50 wt. %, optionally from 60 wt. % to 85 wt. %, based on the total weight of the inorganic particles with secondary particle morphology.
By selecting the first fillers of different crystal forms, it facilitates improving one or more of heat resistance and electrolyte infiltration of the separator.
In some embodiments of the present application, the filler further comprises a second filler, and the second filler is of primary particle morphology. As a result, it can better exert the supporting function of the second filler, improve the heat resistance of the separator, and it can also help the coating layer to have more pore/channel structure and less moisture content when the second filler is present in a relatively low amount.
In some embodiments of the present application, the second filler is present in an amount of ≤50 wt. %, optionally from 1 wt. % to 10 wt. %, based on the total weight of the filler.
In some embodiments of the present application, the second filler has an average particle size Dv50 of from 100 nm to 800 nm, optionally from 200 nm to 400 nm.
In some embodiments of the present application, the second filler has a BET specific surface area of ≤10 m2/g, optionally from 4 m2/g to 9 m2/g.
When one or more of the amount, the average particle size Dv50 and the BET specific surface area of the second filler is within the above ranges, the second filler can better exert the supporting effect, which is conducive to the moisture discharge during the drying process, and results in the coating layer that maintains a suitable porosity and stable pore/channel structure during long-term charge and discharge process, and can further improve the ion transport properties and the electrolyte infiltration of the separator.
In some embodiments of the present application, the second filler comprises inorganic particles with a primary particle morphology, and the inorganic particles with primary particle morphology have a crystal form including one or more of α crystal form and γ crystal form, and optionally have a crystal form including α crystal form. As a result, this can further improve the heat resistance of the separator.
In some embodiments of the present application, the second filler comprises inorganic particles with primary particle morphology, and the inorganic particles with primary particle morphology have a crystal form including α crystal form, and the α crystal form is present in an amount of ≥90 wt. %, optionally from 95 wt. % to 100 wt. %, based on the total weight of the inorganic particles with primary particle morphology.
In some embodiments of the present application, the coating layer further comprises a non-granular binder, and optionally, the non-granular binder comprises an aqueous solution-type binder. As a result, this facilitates the preparation and coating processes of the coating slurry.
In some embodiments of the present application, the non-granular binder in the coating layer is present in an amount of <1 wt. %, based on the total weight of the coating layer. The present application allows the separator to maintain high adhesiveness and good ion transport properties under the premise of reducing the amount of binder.
In some embodiments of the present application, the porous substrate has a thickness of ≤6 μm, optionally from 3 μm to 5 nm. As a result, this contributes to further improving the energy density of the secondary battery.
In some embodiments of the present application, the porous substrate has a porosity of from 32% to 48%, optionally from 34% to 39%. When the porosity of the porous substrate is in the appropriate ranges, it facilitates further improving the ion transport properties of the separator under the premise of ensuring high heat resistance of the separator; at the same time, it can also ensure that the secondary battery has a high discharge rate and reduce self-discharging of the battery.
In some embodiments of the present application, the coating layer has an areal density of from 0.6 g/m2 to 1.5 g/m2, optionally from 0.8 g/m2 to 1.1 g/m2. As a result, this facilitates the formation of a more heat-resistant coating layer.
In some embodiments of the present application, the separator further comprises an adhesive layer, the adhesive layer is disposed on at least part of surface of the coating layer, and the adhesive layer comprises a granular binder, and optionally, the granular binder comprises one or more of a homopolymer or copolymer of acrylate monomer, a homopolymer or copolymer of acrylic monomer, a homopolymer or copolymer of fluorine-containing olefin monomer. The adhesive layer can not only prevent the coating layer from peeling off and improve the safety performance of the secondary battery, but also improve the interface between the separator and the electrode and improve the cycle performance of the secondary battery.
In some embodiments of the present application, the separator has a longitudinal thermal shrinkage rate at 150° C. for 1 h of ≤5%, optionally from 0.5% to 4%.
In some embodiments of the present application, the separator has a lateral thermal shrinkage rate at 150° C. for 1 h of ≤5%, optionally from 0.5% to 4%.
In some embodiments of the present application, the separator has a perforation strength of ≥350 gf, optionally from 370 gf to 450 gf.
In some embodiments of the present application, the separator has a longitudinal tensile strength of ≥2000 kg/cm2, optionally from 2500 kg/m2 to 4500 kg/m2.
In some embodiments of the present application, the separator has a lateral tensile strength of ≥2000 kg/m2, optionally from 2500 kg/m2 to 4500 kg/m2.
In some embodiments of the present application, the separator has an air permeability of ≤300 s/100 mL, optionally from 100 s/100 mL to 200 s/100 mL.
In some embodiments of the present application, the separator has a porosity of from 30% to 45%, optionally from 32% to 36%.
In some embodiments of the present application, the separator has a wetting length of ≥30 mm, optionally from 30 mm to 80 mm.
In some embodiments of the present application, the separator has a wetting speed of ≥3 mm/s, optionally from 3 mm/s to 10 mm/s.
When the performance of the separator satisfies one or more of the above conditions, it is beneficial to improving one or more of energy density, thermal safety performance, capacity exertion and service life of the secondary battery.
A second aspect of the present application provides a method for preparing the separator according to the first aspect of the present application, comprising the following steps: S1, providing a porous substrate; S2, formulating a coating slurry: mixing nanocellulose and a filler in a predetermined proportion in a solvent to prepare the coating slurry; S3, coating: coating one or more surface of the porous substrate with the coating slurry to form a coating layer, and drying to obtain a separator, wherein the separator comprises a porous substrate and a coating layer disposed on one or more surface of the porous substrate, wherein the coating layer comprises nanocellulose and a filler, and the separator has a moisture content of A ppm, the coating layer has a thickness of H um, and the separator satisfies 250≤A/H≤1500. The preparation method of the separator of the present application can provide a coating layer through one coating process, which greatly simplifies the production process of the separator.
In some embodiments of the present application, a coating machine is adopted in the coating step, and the coating machine comprises a gravure roll, and number of lines in the gravure roll is from 100 LPI to 300 LPI, optionally from 125 LPI to 190 LPI.
In some embodiments of the present application, coating speed is from 30 m/min to 120 m/min, optionally from 60 m/min to 90 m/min.
In some embodiments of the present application, a linear speed ratio for the coating layer is from 0.8 to 2.5, optionally from 0.8 to 1.5.
In some embodiments of the present application, drying temperature is from 40° C. to 70° C., optionally from 50° C. to 60° C.
In some embodiments of the present application, drying time is from 10 seconds to 120 seconds, optionally from 20 seconds to 80 seconds.
By controlling the above-mentioned process parameters within the given ranges, the performance of the separator of the present application can be further improved.
In some embodiments of the present application, the method further comprises the step of: S4, secondary coating: coating at least part of surface of the coating layer with a slurry containing a granular binder, and drying to form an adhesive layer.
A third aspect of the present application provides a secondary battery, comprising the separator of the first aspect of the present application or the separator prepared by the method of the second aspect of the present application.
A fourth aspect of the present application provides an electrical device, comprising the secondary battery according to the third aspect of the present application.
The separator of the present application has the characteristics including excellent heat resistance, low moisture content and good electrolyte infiltration, so that a secondary battery using the separator can have the combined characteristics of high energy density, high thermal safety performance, and long service life. The electrical device of the present application comprises the secondary battery provided by the present application, and thus has at least the same advantages as the secondary battery.
In order to explain the technical solutions of the embodiments of the present application more clearly, the following will briefly introduce the drawings that need to be used in the embodiments of the present application. Apparently, the drawings described below are only some embodiments of the present application. A person of ordinary skill in the art can obtain other drawings based on these drawings without creative work.
In the drawings, the drawings are not necessarily drawn to scale. The reference numerals are defined as follows: 1—battery pack; 2—upper case body; 3—lower case body; 4—battery module; 5—secondary battery; 51—housing; 52—electrode assembly; and 53—cover.
Hereafter, embodiments of the separator, the method for preparing the same and the secondary battery and electrical device related thereto of the present application will be specifically described in detail with appropriate references to the accompanying drawings. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known items and repeated descriptions of substantially the same configurations may be omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter described in the claims.
A “range” disclosed herein is defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of end values and may be combined arbitrarily, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is to be understood that ranges of 60-110 and 80-120 are also contemplated. Additionally, if the minimum range values 1 and 2 are listed, and the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 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” represents 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 the range “0-5” is just an abbreviated representation of the combination of these numerical values. In addition, when a parameter is expressed as an integer greater than or equal to 2, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the like.
Unless stated otherwise, all the embodiments and the optional embodiments of the present application can be combined with each other to form a new technical solution, and such a technical solution should be considered to be included in the disclosure of the present application.
Unless stated otherwise, all technical features and optional technical features of the present application can be combined with each other to form a new technical solution, and such a technical solution should be considered to be included in the disclosure of the present application.
Unless stated otherwise, all steps of the present application can be carried out sequentially, and also can be carried out randomly, preferably they are carried out sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed in sequence, or that the method may include steps (b) and (a) performed in sequence. For example, reference to the method further comprising step (c) indicates that step (c) may be added to the method in any order. As an example, the method may comprise steps (a), (b) and (c), steps (a), (c) and (b), or steps (c), (a) and (b), and the like.
Unless stated otherwise, the transition phases “comprising” and “including” mentioned in the present application means that it is drafted in an open mode or in a close mode. For example, the transition phases “comprising” and “including” may mean that other components not listed may also be included or contained, or only the listed components may be included or contained.
In the present application herein, unless otherwise stated, the term “or” is inclusive. For example, the phrase “A or B” means “A, B, or both A and B.” More specifically, any of the following conditions satisfy the condition “A or B”: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).
In this application, the terms “plurality”, “a plurality of” and “multiple” and “several” refer to two or more.
Unless otherwise specified, the terms used in this application have the well-known meanings generally understood by those skilled in the art.
Unless otherwise specified, a numerical value for each parameter mentioned in the present application can be determined by various test methods commonly used in the art, for example, can be determined according to the test methods given in the Examples of the present application.
Normally, a secondary battery comprises an electrode assembly and an electrolyte, and the electrode assembly comprises a positive electrode plate, a negative electrode plate and a separator, the separator is disposed between the positive electrode plate and the negative electrode plate and is mainly used to prevent short circuit between positive electrode and negative electrode and meanwhile allows active ions to pass through to form a circuit. With the application and promotion of secondary batteries, the requirements for energy density of secondary battery are getting higher and higher. To obtain a thinner separator is an effective measure to increase energy density of secondary batteries. Currently, the separators used in commercial secondary batteries are usually polyolefin porous films, such as polyethylene porous films, polypropylene porous films or polypropylene/polyethylene/polypropylene three-layer composite films, with melting points between 130° C. and 160° C. As a result, when the thickness of the separator is reduced, the heat resistance of the separator will deteriorate, and the separator will shrink severely when heated, thereby increasing the risk of short circuit between positive electrode and negative electrode.
In order to solve the above problems, the current measures are mainly to apply a heat-resistant inorganic ceramic layer on the polyolefin porous film, which can increase the mechanical strength of the separator, reduce the shrinkage of the separator when heated, and reduce the risk of short circuit between positive electrode and negative electrode. However, commercially available inorganic ceramic particles have relatively large particle size, thus will increase the overall thickness of the separator, resulting in the inability to balance the energy density of secondary batteries, especially in the field of power batteries, which is not conducive to increasing the cruising range. In addition, due to the relatively large particle size of inorganic ceramic particles, the number of layers laminated on the polyolefin porous film is reduced (usually ≤5 layers), which results in limited improvement in the heat resistance of the separator. Nanosizing inorganic ceramic particles can reduce the thickness of the coating and alleviate the adverse impact on the energy density of secondary batteries. However, the coating formed by nanosized inorganic ceramic particles has low porosity and the nanosized inorganic ceramic particles will easily block the micropores of the polyolefin porous film, thus leading to the reduction of overall porosity of the separator and an increase of the ionic impedance of the separator, and inhibiting active ion transport. Meanwhile, due to the high specific surface area of nanosized inorganic ceramic particles and the contact between particles being point contact, a large amount of binder is required to ensure the adhesiveness between particles, whereas the large amount of binder will lead to the problem of blocking pores, which is detrimental to the rate performance of the secondary battery, for example, the easy formation of dendrites on the surface of the negative electrode, which is in turn further detrimental to the capacity and energy density of secondary batteries.
In addition, inorganic ceramic particles have the characteristic of easily adsorbing water, especially for the nanosized inorganic ceramic particles due to the significantly increased specific surface area, which leads to a significant increase in the moisture content of the separator. During the long-term charging and discharging process of secondary batteries, the moisture in the isolation film will gradually be released and enter the electrolyte. At present, the most widely used commercial electrolyte system is the mixed carbonate solution of lithium hexafluorophosphate which has poor thermal stability in high temperature environment and will decompose to form PF5 at relatively high temperature. PF5 has a high sensitivity to trace amounts of water in the electrolyte and when it encounters water, it generates HF, which increases the acidity of the electrolyte and can easily corrode the positive electrode active material and the positive electrode current collector, causing the dissolution of transition metal ions in the positive electrode active material, thereby affecting the electrochemical performance of the secondary battery. Therefore, the separator is also required to have a low moisture content.
With the application and promotion of secondary batteries, the requirements for service life of secondary battery are getting higher and higher. In the long-term charging and discharging process of the secondary battery, the separator gradually dries up and fails, which is an important reason for the capacity decline of the secondary battery. This is because the internal resistance of the battery increases after the separator dries up, which leads to the incomplete charging and discharging, and then leads to the rapid decay of the capacity of the secondary battery, which greatly reduces the service life of the secondary battery. Therefore, the separator is also required to have good electrolyte infiltration.
However, the existing separator is often difficult to have the combined characteristics of high heat resistance, low moisture content and good electrolyte infiltration.
The inventors of the present application have unexpectedly found through the in-depth research that by disposing a coating layer comprising nanocellulose and a filler on surface of the porous substrate of the separator and reasonably controlling the ratio of the moisture content of the separator to the thickness of the coating layer, the separator can have the combined characteristics of high heat resistance, low moisture content and good electrolyte infiltration, and further the secondary battery can have the combined characteristics of high energy density, high thermal safety performance and long service life.
In particular, the first aspect of embodiments of the present application provides a separator, comprising a porous substrate and a coating layer disposed on one or more surface of the porous substrate, wherein the coating layer comprises nanocellulose and a filler, and the separator has a moisture content of A ppm, the coating layer has a thickness of H μm, and the separator satisfies 250≤A/H≤1500.
The inventors of the present application have unexpectedly found, through a lot of research, that by disposing a coating layer comprising nanocellulose and a filler on one or more surface of the porous substrate of the separator and controlling the ratio of the moisture content of the separator to the thickness of the coating layer within the above-mentioned specific range, the separator can have the combined characteristics of high heat resistance, low moisture content and good electrolyte infiltration.
Nanocellulose is rich in hydroxyl groups, which makes it have strong hydrophilicity. Therefore, using nanocellulose alone easily leads to high moisture content in the separator, which affects the electrochemical performance of secondary batteries. The coating layer of the present application comprises nanocellulose and a filler at the same time, and the nanocellulose and filler can make contact to form a stable spatial network structure, which is beneficial to water discharge in the drying process, thereby enabling the separator of the present application to have lower moisture content.
The inventors of the present application have found, through numerous studies, that when the moisture content A ppm of the separator containing nanocellulose and a filler and the thickness H μm of the coating layer are controlled to satisfy A/H being between 250 and 1500, the coating layer can have a good spatial network structure and a suitable content of hydroxyl functional groups, so that the separator can have both low moisture content and good electrolyte infiltration, and the secondary battery using the separator can have good electrochemical performance, in particular, a long cycle life and a long storage life. In addition, the coating layer of the present application simultaneously comprises nanocellulose and a filler, and the nanocellulose and filler can make contact together to enable the coating layer to have a stable spatial network structure, thus the coating layer further has high heat resistance, can reduce the shrinkage degree of the separator when heated, reduce the risk of short circuit between positive electrode and negative electrode, thereby resulting in the secondary battery having high thermal safety performance; At the same time, because the coating layer of the present application has high heat resistance, a thinner porous substrate can be used, thus the secondary battery can further have high energy density.
The moisture content A ppm of the separator and the thickness H μm of the coating satisfy the requirements of 250≤A/H≤1500. For example, A/H may be 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1250, 1500 or in any of the ranges formed by the above values. Optionally, 300≤A/H≤1500, 500≤A/H≤1500, 500≤A/H≤1250, 500≤A/H≤1100, 500≤A/H≤1000, 600≤A/H≤1250, 600≤A/H≤1100 or 600≤A/H≤1000. As a result, this facilitates the coating layer having more stable spatial network structure and more suitable content of hydroxyl functional groups, so that the separator can have the combined characteristics of high heat resistance, low moisture content and good electrolyte infiltration, and the secondary battery can have the combined characteristics of high thermal safety performance, long cycle life and long storage life.
The moisture content of the separator may be measured by a moisture tester, and the test method may be Karl Fischer moisture testing method, and the test instrument can be Metrohm 831 Karl Fischer moisture tester.
In some embodiments, the moisture content A ppm of the separator satisfies A≤1000. As a result, less moisture is dissolved from the separator and released into the electrolyte during the charging and discharging process of secondary battery, thereby contributing to good electrochemical performance of the secondary battery. In particular, the secondary battery can have high capacity exertion and low volume expansion rate.
In addition, the inventors of the present application also unexpectedly discovered in the research process that the moisture content of the separator is not as low as possible; when the moisture content of the separator is too low, for example, lower than 400 ppm, the interface properties between the separator and the electrolyte become worse, for example, the liquid absorption of the separator decreases, and the infiltration properties of the electrolyte become worse. As a result, during the long-term charging and discharging process of secondary battery, the separator will quickly dry up and fail, which will lead to the rapid increase of internal resistance, rapid decay of capacity and greatly shorten service life of the secondary battery.
In some embodiments, the moisture content A ppm of the separator satisfies 400≤A≤1000. For example, A may be 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 850, 1000, or in any of the ranges formed by the above values. Optionally, 400≤A≤900, 400≤A≤800, 400≤A≤700, 400≤A≤600, 500≤A≤900, 500≤A≤800 or 500≤A≤700. As a result, this facilitates the coating layer having more stable spatial network structure and more suitable content of hydroxyl functional groups, so that the separator can better have combined characteristics of high heat resistance, low moisture content and good electrolyte infiltration and can further improve the cycle life and storage life of the secondary battery.
In some embodiments, the thickness H u m of the coating satisfies 0<H≤1.5. For example, H may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 or any of the ranges formed by the above values. Optionally, 0<H≤1.4, 0<H≤1.3, 0<H≤1.2, 0<H≤1.1, 0<H≤1.0, 0<H≤0.9, 0<H≤0.8, 0.1≤H≤0.8, 0.2≤H≤0.8, 0.3≤H≤0.8, 0.4≤H≤0.8 0.5≤H≤0.8. As a result, this contributes to improving the energy density of the secondary battery.
In some embodiments, the coating layer has an areal density of from 0.6 g/m2 to 1.5 g/m2, optionally from 0.8 g/m2 to 1.1 g/m2. As a result, this facilitates the formation of a more heat-resistant coating layer.
In some embodiments, the porous substrate may have a thickness of ≤6 μm, optionally from 3 μm to 5 nm. The coating layer of the present application may significantly improve the heat resistance of the separator, so that a thinner porous substrate can be used, thus contributing to further improving the energy density of the secondary battery.
In some embodiments, the porous substrate has a porosity of from 32% to 48%, optionally from 34% to 39%. When the porosity of the porous substrate is in the appropriate ranges, it facilitates further improving the ion transport properties of the separator under the premise of ensuring high heat resistance of the separator; at the same time, it can also ensure that the secondary battery has a high discharge rate and reduce self-discharging of the battery.
The material of the porous substrate is not specially limited in the present application, and the porous substrate may be any known substrate with good chemical and mechanical stability; for example, the porous substrate may include one or more of a porous polyolefin-based resin film (e.g. one or more of polyethylene, polypropylene, and polyvinylidene fluoride), a porous glass fiber, and a porous non-woven fabric. The porous substrate may be a single-layer film or a multilayer film. When the porous substrate is a multilayer composite film, the materials of individual layers may be the same or different.
Another direction of increasing the energy density of secondary batteries is to increase the voltage, for example, using high-voltage positive electrode active materials. However, increasing the voltage will have a significant impact on the stability of the separator, and thus requires the separator to have good voltage breakdown resistance property. The coating layer of the separator of this application includes nanocellulose, which is a general term for cellulose with any one dimensional size of nano-scale (e.g., 100 nm or lower). The nanocellulose has the properties of both cellulose and nano-particles. Nanocellulose may be a polymer nanomaterial extracted from wood, cotton, and other materials in nature through one or more means in chemistry, physics, biology, etc. It has the advantages of wide sources, low cost, biodegradability, high modulus and high specific surface area, so it is an excellent substitute for traditional petrochemical resources and can effectively alleviate environmental pollution and shortage of petrochemical resources. Nanocellulose also has good high temperature resistance, and relatively small volume change after being heated, which can improve the heat resistance of the separator; at the same time, compared with traditional inorganic ceramic particles, nanocellulose has smaller density, which may further reduce the weight of secondary batteries and improve the weight energy density of secondary batteries. In addition, nanocellulose also helps to make the coating have tiny and uniform nano-pores and prevent current leakage, thus allowing the separator to have both high ion transport properties and good voltage breakdown resistance property.
In some embodiments, the nanocellulose may comprise one or more of cellulose nanofibers (CNF, also referred to as nanofibril cellulose or microfibril cellulose), cellulose nanowhiskers (CNC, also referred to as cellulose nanocrystals, nanocrystalline cellulose), and bacterial nanocellulose (BNC, also referred to as bacterial cellulose or microbial cellulose), and optionally is cellulose nanowhiskers. The cellulose nanowhiskers may have higher crystallinity, thereby reducing their hydrophilicity, which in turn facilitates moisture discharge during the drying process and thus results in lower moisture content in the separator of the present application. In addition, cellulose nanowhiskers may easily make contact with the filler, which allows the coating layer to have a more stable spatial network structure, thereby further improving the performance of the separator.
In some embodiments, the nanocellulose may comprise one or more of unmodified nanocellulose (also referred to as hydroxyl nanocellulose) and modified nanocellulose, and optionally is modified nanocellulose.
The modified nanocellulose comprises a modifying group. In some embodiments, the modifying group may comprise one or more of an amino group, a carboxylic acid group, an aldehyde group, a sulfonic acid group, a boric acid group, and a phosphoric acid group, and optionally comprises one or more of a sulfonic acid group, a boric acid group, and a phosphoric acid group.
In further research, the inventors have found that when the nanocellulose has the above-mentioned specific modifying groups, on one hand, the modifying groups can effectively improve the heat resistance of the separator and improve the thermal safety performance of the secondary battery; on another hand, the modifying groups further facilitates a separator having a lower moisture content under the premise of good electrolyte infiltration, thereby further improving the electrochemical performance of the secondary battery.
When the nanocellulose has the above-mentioned specific modifying groups, the nanocellulose may further form a more stable spatial network structure with the filler, which may further improve the ion transport property and voltage breakdown resistance properties of the separator, thereby being beneficial to matching with the high-voltage positive electrode active materials and further improving the energy density of the secondary battery.
In addition, the presence of modifying groups may further reduce the proportion of hydroxyl groups, which can ensure that the coating slurry has an appropriate viscosity and is thus more conducive to coating process, thereby improving the production efficiency of separator and the uniformity of coating layer.
In some embodiments, the modified nanocellulose comprises a hydroxyl group and a modifying group, and a molar ratio of the modifying group to the hydroxyl group may be from 1:4 to 4:1, optionally from 2:3 to 7:3. When the molar ratio of the modifying group to the hydroxyl group is in the appropriate ranges, the heat resistance and ion transport properties of the separator may be further improved, and the separator has a lower moisture content. In addition, it can effectively avoid the following situations: when the molar ratio of the modifying group to the hydroxyl group is too small, the further improvement effect of the modifying group on the heat resistance and ion transport property of the separator may not be apparent; when the molar ratio of modifying group to hydroxyl group is too high, the electrolyte infiltration of the separator may be impacted, for example, the ion transport property of the separator may become worse, which may affect the cycle life and storage life of the secondary battery and may also lead to the decline of the heat resistance of the separator, and may further affect the thermal safety performance of the secondary battery.
The types of modifying group in nanocellulose may be determined by infrared spectroscopy. For example, the infrared spectrum may be used for test a material by determine the characteristic peaks contained in the material, thus determining the types of modifying group. Specifically, instruments and methods known in the field, for example an infrared spectrometer (such as IS10 Fourier transform infrared spectrometers of Nicolet Company in the United States), may be used for performing an analysis of infrared spectrum of a material according to GB/T 6040-2019 General Rules for Infrared Analysis.
In some embodiments, the nanocellulose has an aspect ratio of from 5 to 80, optionally from 10 to 40. When the aspect ratio of the nanocellulose is in the appropriate ranges, the heat resistance and ion transport properties of the separator may be further improved. In addition, it can effectively avoid the following situations: when the aspect ratio of nanocellulose is too small, the making-contact effect between nanocellulose and filler is relatively poor, and the heat resistance of the coating layer may become worse; in the drying process of the coating layer, part of nanocellulose may easily collapse due to lack of the supporting function of filler, and then easily lead to pore plugging problems, and thus also hinder active ion transport and water discharge, and affect the cycle performance and capacity exertion of the secondary battery; when the aspect ratio of nanocellulose is too high, the nanopores in the coating layer formed by contacting nanocellulose with filler are small, which may also lead to the deterioration of ion transport property of the separator.
In some embodiments, the nanocellulose has an average diameter of from 10 nm to 40 nm, optionally from 10 nm to 35 nm. When the average diameter of the nanocellulose is within the appropriate ranges, the heat resistance, ion transport property and voltage breakdown resistance property of the separator may be further improved. In addition, it can effectively avoid the following situations: when the average diameter of nanocellulose is too high, the nanopores in the coating layer formed by contacting nanocellulose with filler are relatively large, which may lead to poor voltage breakdown resistance of the separator; at the same time, the making-contact effect between nanocellulose and filler is relatively poor, and the heat resistance of the coating layer may become worse; in the drying process of the coating layer, part of nanocellulose may easily collapse due to lack of the supporting function of filler, and then easily lead to pore plugging problems, and thus also hinder active ion transport and water discharge, and affect the cycle performance and capacity of the secondary battery.
In some embodiments, the nanocellulose has an average length of from 100 nm to 600 nm, optionally from 200 nm to 500 nm. When the average length of the nanocellulose is in the appropriate ranges, the heat resistance and ion transport properties of the separator may be further improved. In addition, it can effectively avoid the following situations: when the average length of nanocellulose is too small, the making-contact effect between nanocellulose and filler is relatively poor, and the heat resistance of the coating layer may become worse; in the drying process of the coating layer, part of nanocellulose may easily collapse due to lack of the supporting function of filler, and then easily lead to pore plugging problems, and thus also hinder active ion transport and water discharge, and affect the cycle performance and capacity exertion of the secondary battery; when the average length of nanocellulose is too high, the coating slurry has high viscosity and poor flow, which may affect the application of coating slurry and thus the coating quality of coating slurry, such as heat resistance and ion transport properties of the separator.
The average length and average diameter of nanocellulose may be measured by the following method: cutting a sample of 3.6 mm×3.6 mm from any area of the separator, mapping the micro-morphology and structure of the coating layer in the sample by scanning electron microscope (such as ZEISS Sigma 300) using high vacuum mode and a working voltage of 3 kV and magnification of 30,000 times, to obtain SEM images; selecting several (for example, 5 or more) test areas for statistically recording lengths according to the obtained SEM images, with each test area having a size of 0.5 μm×0.5 μm, and then taking the average of the lengths obtained from individual test areas as the average length of nanocellulose; selecting several (for example, 5 or more) test areas for statistically recording diameters using Nano Measurer particle size distribution statistics software according to the obtained SEM images, with each test area having a size of 0.5 μm×0.5 μm, and then taking the average of the diameters obtained from individual test areas as the average diameter of nanocellulose.
In some embodiments, the nanocellulose may have a weight average molecular weight of from 10000 to 60000, optionally from 30000 to 50000.
In some embodiments, the nanocellulose may have an equilibrium degree of polymerization of from 150 DP to 300 DP, optionally from 200 DP to 250 DP.
When the weight average molecular weight and/or degree of polymerization of nanocellulose is/are in the appropriate ranges, not only nanocellulose may be prevented from blocking the pore/channel structure of the separator, but also the viscosity of the coating slurry may be in an appropriate range. As a result, the slurry may have better fluidity and infiltration during coating, which is more conducive to improving the quality of the coating layer. For example, the heat resistance and ion transport properties of the separator may be further improved.
In some embodiments, the nanocellulose may have a shape including one or more of tubular (e.g. hollow tubular), fibrous shape and rod shape. Appropriate shape of nanocellulose is more conducive to the formation of a stable spatial network structure by contacting with filler, which can further improve the ion transport property and external force extrusion resistance of the separator.
In some embodiments, the nanocellulose in the coating layer may be present in an amount of from 6 wt. % to 35 wt. %, optionally from 10 wt. % to 30 wt. %, based on the total weight of the coating layer. When the amount of nanocellulose is in the appropriate ranges, it can ensure that the coating slurry has an appropriate viscosity, which is more conducive to coating process, and is also conducive to the lower moisture content and good electrolyte infiltration of the separator; in addition, it is also conducive to the formation of a stable spatial network structure by contacting the nanocellulose with the filler. As a result, the performance of the separator may be further improved, such as reducing the moisture content of the separator, and improving the heat resistance, ion conduction ability, external force extrusion resistance and voltage breakdown resistance of the separator.
In some embodiments, the filler in the coating layer may be present in an amount of ≥60 wt. %, optionally from 65 wt. % to 90 wt. %, based on the total weight of the coating layer. When the amount of filler is in the appropriate ranges, it can ensure that the coating slurry has an appropriate viscosity, which is more conducive to coating process, and is also conducive to the lower moisture content and good electrolyte infiltration of the separator; in addition, it is also conducive to the formation of a stable spatial network structure by contacting with the nanocellulose, thereby further improving the performance of the separator, such as reducing the moisture content of the separator, and improving the heat resistance, tensile strength, puncture resistance and external force extrusion resistance of the separator.
During the long-term charging and discharging of the secondary battery, the volume of the whole battery will increase due to the irreversible changes of microstructure of the positive electrode active materials and negative electrode active materials. Especially, when the secondary battery is charged rapidly, the increase of the volume of the negative electrode active materials is higher after the intercalation of active ions. After the expansion of the battery, the separator will be squeezed and/or stretched, which will easily lead to the damage of the separator and thus increase the risk of short circuit between positive electrode and negative electrode. Therefore, the separator is also required to have good external force extrusion resistance. The presence of fillers helps the coating layer to have a stable spatial network structure, which may improve the ion transport property and heat resistance of the separator; In addition, it may also improve the tensile strength, puncture resistance and external force extrusion resistance of the separator.
In some embodiments, the filler may comprise one or more of inorganic particles and organic particles.
In some embodiments, optionally, the decomposition temperature of the filler is 200° C. or higher, the filler may have good thermal stability property and be not easily decomposed, thereby further improving the heat resistance of the separator.
Inorganic particles have good thermal stability property and cannot be easily decomposed, and usually have hydroxyl groups on their surfaces, so they can easily make contact with nanocellulose to form a stable spatial network structure. In some embodiments, optionally, the inorganic particles include one or more of inorganic particles with a dielectric constant of 5 or more, inorganic particles with ion conductivity but without ion storage capability, and inorganic particles capable of undergoing electrochemical reactions.
Optionally, the inorganic particles with a dielectric constant of 5 or more comprise one or more of oehmite, alumina, zinc oxide, silicon oxide, titanium oxide, zirconium oxide, barium oxide, calcium oxide, magnesium oxide, nickel oxide, tin oxide, cerium oxide, yttrium oxide, hafnium oxide, aluminum hydroxide, magnesium hydroxide, silicon carbide, boron carbide, aluminum nitride, silicon nitride, boron nitride, magnesium fluoride, calcium fluoride, barium fluoride, barium sulfate, magnesium aluminum silicate, lithium magnesium silicate, sodium magnesium silicate, bentonite, hectorite, zirconium titanate, barium titanate, Pb(Zr,Ti)O3 (abbreviated as PZT), Pb1-mLamZr1-nTinO3 (abbreviated as PLZT, 0<m<1, 0<n<1), Pb(Mg3Nb2/3)O3—PbTiO3 (abbreviated as PMN-PT) and their respective modified inorganic particles. Optionally, the modification mode of each inorganic particle may be chemical modification and/or physical modification. The chemical modification mode includes coupling agent modification (by using for example silane coupling agent, titanate coupling agent, etc.), surfactant modification, and polymer grafting modification, etc. The physical modification mode may be mechanical force dispersion, ultrasonic dispersion, high-energy treatment and the like. Through modification treatment, the agglomeration of inorganic particles may be reduced, thus forming a more stable and uniform spatial network structure by contacting inorganic particles with nanocellulose; in addition, by modifying inorganic particles with surface active materials or polymer or coupling agents with specific functional groups, it also helps to improve the infiltration of the electrolyte to the coating layer and the adhesiveness of the coating layer.
Optionally, the inorganic particles with ion conductivity but without ion storage capability comprise one or more of Li3PO4, lithium titanium phosphate Lix1Tiy1(PO4)3, lithium aluminum titanium phosphate Lix2Aly2Tiz1(PO4)3, (LiAlTiP)x3Oy3 type glass, lithium lanthanum titanate Lix4Lay4TiO3, lithium germanium thiophosphate Lix5Gey5Pz2Sw, lithium nitride Lix6Ny6, SiS2 type glass Lix7Siy7Sz3 and P2S5 type glass Lix8Py8Sz4, wherein 0<x1<2, 0<y1<3, 0<x2<2, 0<y2<1, 0<z1<3, 0<x3<4, 0<y3<13, 0<x4<2, 0<y4<3, 0<x5<4, 0<y5<1, 0<z2<1, 0<w<5, 0<x6<4, 0<y6<2, 0<x7<3, 0<y7<2, 0<z3<4, 0<x8<3, 0<y8<3, 0<z4<7. As a result, this can further improve the ion transport property of the separator.
Optionally, the inorganic particles capable of undergoing electrochemical reactions comprise one or more of lithium-containing transition metal oxides, lithium-containing phosphates, carbon-based materials, silicon-based materials, tin-based materials, and lithium-titanium compounds.
Organic particles have good thermal stability property and cannot be easily decomposed, which can improve the heat resistance of the separator; at the same time, when the internal temperature of the secondary battery reaches the melting point of organic particles due to overcharge abuse and heat abuse, the organic particles may melt and be sucked into the micropores of the porous substrate due to capillary action, which results in closing pores and breaking circuits and thus facilitates the high safety performance of the secondary battery.
In some embodiments, the organic particles comprise, but are not limited to, one or more of polyethylene particles, polypropylene particles, polystyrene particles, cellulose, cellulose modifiers (e.g. carboxymethylcellulose), melamine resin particles, phenolic resin particles, polyester particles (e.g. polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate), organic silicon resin particles, polyimide particles, polyamide imide particles, polyarylamide particles, polyphenylene sulfide particles, polysulfone particles, polyethersulfone particles, polyetheretherketone particles, polyaryletherketone particles, and copolymers of butyl acrylate and ethyl methacrylate (e.g. crosslinked polymers of butyl acrylate and ethyl methacrylate).
In some embodiments, optionally, the glass transition temperature of the organic particles may be 130° C. or higher. Therefore, when the internal temperature of the secondary battery reaches 130° C., the organic particles will not change from the glassy state to the viscous flow state, thus ensuring that the separator does not shrink violently. Optionally, the organic particles comprise, but are not limited to, one or more of melamine formaldehyde resin particles, phenolic resin particles, polyester particles, organic silicon resin particles, polyimide particles, polyamide imide particles, polyarylamide particles, polyphenylene sulfide particles, polysulfone particles, polyethersulfone particles, polyetheretherketone particles, and polyaryletherketone particles.
In some embodiments, the filler comprises a first filler, and the first filler is of secondary particle morphology formed by agglomeration of primary particles. The filler with secondary particle morphology has relatively high specific surface area and better affinity with nanocellulose, and the nanocellulose can also make contact in the gap between the primary particles for forming the filler with secondary particle morphology, so that the nanocellulose and the first filler make contact to form an integrated effect, and the resulting coating layer may have a more stable spatial network structure and thus the separator may have a suitable porosity and a stable pore/channel structure, meanwhile the separator may have the combined characteristics of low moisture content and good electrolyte infiltration.
In some embodiments, the first filler is present in an amount of from 50 wt. % to 100 wt. %, optionally from 90 wt. % to 99 wt. %, based on the total weight of the filler. When the content of the first filler is in a suitable range, it is beneficial to contacting with nanocellulose to form an integrated effect, so that the coating layer can have a more stable spatial network structure, thereby further improving the heat resistance, tensile strength, puncture resistance and external force extrusion resistance of the separator.
In some embodiments, the first filler has an average particle size Dv50 of ≤200 nm, optionally from 50 nm to 200 nm. As a result, the first filler has a relatively high specific surface area, which increases the affinity between the first filler and the nanocellulose, and facilitates contacting the first filler with the nanocellulose to form an integrated effect, and thus the resulting coating layer may have a more stable spatial network structure and the separator may have better heat resistance and electrolyte infiltration.
In some embodiments, the first filler has a BET specific surface area of >20 m2/g, optionally from 25 m2/g to 50 m2/g. As a result, the first filler has better affinity with nanocellulose, which facilitates contacting with the nanocellulose to form an integrated effect, and thus the resulting coating layer may have a more stable spatial network structure, meanwhile the separator may have better heat resistance and electrolyte infiltration.
In some embodiments, the first filler comprises inorganic particles with secondary particle morphology, and the inorganic particles with secondary particle morphology have a crystal form including at least two of α crystal form, θ crystal form, γ crystal form and η crystal form, optionally have a crystal form including at least two of α crystal form, θ crystal form, and γ crystal form.
In the X-ray diffraction spectra measured by using an X-ray diffraction meter, the inorganic particles with secondary particle morphology of α crystal form have diffraction peaks at 2θ of 57.48°±0.2° and 43.34°±0.2°. In some embodiments, the α crystal form is present in an amount of ≥1.2 wt. %, optionally from 1.2 wt. % to 10 wt. %, more optionally from 1.2 wt. % to 5 wt. %, based on the total weight of the inorganic particles with secondary particle morphology.
In the X-ray diffraction spectra measured by using an X-ray diffraction meter, the inorganic particles with secondary particle morphology of θ crystal form have diffraction peaks at 2θ of 36.68°±0.2° and 31.21°±0.2°. In some embodiments, the θ crystal form is present in an amount of ≥50 wt. %, optionally from 60 wt. % to 85 wt. %, more optionally from 60 wt. % to 82.5 wt. %, based on the total weight of the inorganic particles with secondary particle morphology.
In the X-ray diffraction spectra measured by using an X-ray diffraction meter, the inorganic particles with secondary particle morphology of γ crystal form have diffraction peaks at 2θ of 66.95°±0.2° and 45.91°±0.2°. In some embodiments, the γ crystal form is present in an amount of ≥10 wt. %, optionally from 15 wt. % to 60 wt. %, more optionally from 15 wt. % to 35 wt. %, based on the total weight of the inorganic particles with secondary particle morphology.
In the X-ray diffraction spectra measured by using an X-ray diffraction meter, the inorganic particles with secondary particle morphology of η crystal form have diffraction peaks at 2θ of 31.89°±0.2° and 19.37°±0.2°. In some embodiments, the η crystal form is present in an amount of ≤5 wt. %, optionally ≤2 wt. %, more optionally ≤1 wt. %, based on the total weight of the inorganic particles with secondary particle morphology.
Inorganic particles with secondary particle morphology of α crystal form have the advantages of high hardness, good heat resistance, low dielectric constant, high safety and high true density; inorganic particles with secondary particle morphology of θ crystal form have moderate specific surface area and hardness, which can better improve the heat resistance and ion transport characteristics of the separator at the same time; inorganic particles with the secondary morphology of γ crystal form and η crystal form have the advantage of large specific surface area. Thus, by selecting the first fillers of different crystal forms, it facilitates improving one or more of heat resistance and electrolyte infiltration of the separator.
In some embodiments, the first filler comprises inorganic particles with secondary particle morphology, and the inorganic particles with secondary particle morphology have a crystal form including θ crystal form, and the θ crystal form is present in an amount of ≥50 wt. %, optionally from 60 wt. % to 85 wt. %, more optionally from 60 wt. % to 82.5 wt. %, based on the total weight of the inorganic particles with secondary particle morphology.
In some embodiments, the first filler comprises inorganic particles with secondary particle morphology, and the inorganic particles with secondary particle morphology have a crystal form including α crystal form, θ crystal form, γ crystal form and η crystal form, and the α crystal form is present in an amount of 1.2 wt. % to 5 wt. %, the θ crystal form is present in an amount of from 60 wt. % to 82.5 wt. %, the γ crystal form is present in an amount of from 15 wt. % to 35 wt. %, and the θ crystal form is present in an amount of ≤1 wt %, based on the total weight of the inorganic particles with secondary particle morphology.
The X-ray diffraction spectrum of the inorganic particles with the secondary particle morphology can be obtained by testing the following process including: oven drying the inorganic particles with the secondary particle morphology, milling in a mortar (such as an agate mortar) for 30 minutes, and then testing using an X-ray diffractometer (such as a Miniflex 600-C) to obtain the X-ray diffraction spectrum. Cu target, Ni filter, tube pressure of 40 KV, tube flow of 15 mA, and continuous scanning range of from 5° to 80° may be used during the test.
In some embodiments, the first filler comprises inorganic particles with secondary particle morphology, and the inorganic particles with secondary particle morphology can be prepared by the following process including: subjecting a precursor solution of the inorganic particles to an oxidation reaction by high pressure sputtering, then heating at 600° C. to 900° C. (for example, from 1 hour to 3 hours) to form small particles, and then drying at 150° C. to 250° C. (for example, from 30 minutes to 60 minutes) to obtain the inorganic particles with secondary particle morphology.
In some embodiments, the filler further comprises a second filler, and the second filler is of primary particle morphology. The filler with primary particle morphology has a larger particle size and higher strength, which can better exert its supporting role in the coating layer and reduce the amount of binder and improve the heat resistance of the separator; and it also helps the separator to have more pore/channel structure and less moisture content when the second filler is present in a relatively low amount, thereby further improving the ion transport characteristics and the electrolyte infiltration.
In some embodiments, the second filler is present in an amount of ≤50 wt. %, optionally from 1 wt. % to 10 wt. %, based on the total weight of the filler. As a result, the second filler can better exert the supporting effect, which is conducive to the moisture discharge during the drying process, and results in the coating layer that maintains a suitable porosity and stable pore/channel structure during long-term charge and discharge process, and can further improve the ion transport properties and the electrolyte infiltration of the separator.
In some embodiments, the second filler has an average particle size Dv50 of from 100 nm to 800 nm, optionally from 200 nm to 400 nm; As a result, the second filler can better exert the supporting effect, which is conducive to the moisture discharge during the drying process, and results in the coating layer that maintains a suitable porosity and stable pore/channel structure during long-term charge and discharge process, and can further improve the ion transport properties and the electrolyte infiltration of the separator.
In some embodiments, the second filler has a BET specific surface area of ≤10 m2/g, optionally from 4 m2/g to 9 m2/g. As a result, the second filler can better exert the supporting effect, which is conducive to the moisture discharge during the drying process, and results in the coating layer that maintains a suitable porosity and stable pore/channel structure during long-term charge and discharge process, and can further improve the ion transport properties and the electrolyte infiltration of the separator.
In some embodiments, the second filler comprises inorganic particles with primary particle morphology, and the inorganic particles with primary particle morphology have a crystal form including one or more of α crystal form and γ crystal form, and optionally have a crystal form including α crystal form. Inorganic particles with primary particle morphology of α crystal form have the advantages of high hardness, good heat resistance, low dielectric constant, high safety and high true density, which can better improve the heat resistance of the separator.
In some embodiments, the second filler comprises inorganic particles with primary particle morphology, and the inorganic particles with primary particle morphology have a crystal form including α crystal form, and the α crystal form is present in an amount of ≥90 wt. %, optionally from 95 wt. % to 100 wt. %, based on the total weight of the inorganic particles with primary particle morphology.
In some embodiments, the coating layer may further comprise a non-granular binder. The type of the non-granular binder is not particularly limited in the present application, and any well-known material having good adhesiveness can be selected. Optionally, the non-granular binder comprises an aqueous solution-type binder, which has the advantages of good thermodynamic stability and environmental protection, thereby facilitating the preparation and application of the coating slurry. As an example, the aqueous solution-type binder includes one or more of an aqueous solution-type acrylic resin (for example, acrylic acid, methacrylic acid, sodium acrylate monomer homopolymer or copolymer with other comonomers), polyvinyl alcohol (PVA), isobutylene-maleic anhydride copolymer, and polyacrylamide.
Optionally, the non-granular binder in the coating layer is present in an amount of <1 wt. %, based on the total weight of the coating layer. The nanocellulose and the filler in the coating layer of the present application can form a stable spatial network structure, thereby enabling the separator to maintain high adhesiveness and good ion transport properties under the premise of reducing the amount of binder.
In some embodiments, the separator may further comprise an adhesive layer, the adhesive layer is disposed on at least part of surface of the coating layer, and the adhesive layer comprises a granular binder. The adhesive layer can not only prevent the coating layer from peeling off and improve the safety performance of the secondary battery, but also improve the interface between the separator and the electrode and improve the cycle performance of the secondary battery.
Optionally, the granular binder comprises one or more of a homopolymer or copolymer of acrylate monomer, a homopolymer or copolymer of acrylic monomer, a homopolymer or copolymer of fluorine-containing olefin monomer. The comonomer includes, but is not limited to, one or more of an acrylate monomer, an acrylic monomer, an olefin monomer, a halogen-containing olefin monomer, a fluoroether monomer, and the like.
Optionally, the granular binder comprises a vinylidene fluoride-based polymer, such as a homopolymer of vinylidene fluoride monomer (VDF) and/or a copolymer of vinylidene fluoride monomer and a comonomer. The comonomer may be one or more of an olefin monomer, a fluorine-containing olefin monomer, a chlorine-containing olefin monomer, an acrylate monomer, an acrylic monomer, and a fluoroether monomer. Optionally, the comonomer may comprise one or more of trifluoroethylene (VF3), chlorotrifluoroethylene (CTFE), 1,2-difluoroethylene, tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro(alkylvinyl) ethers such as perfluoro(methylvinyl) ether (PMVE), perfluoro(ethylvinyl) ether (PEVE), perfluoro(propylvinyl) ether (PPVE), perfluoro(1,3-dioxole), and perfluoro(2,2-dimethyl-1,3-dioxole) (PDD).
In some embodiments, the separator has a longitudinal (also referred to as “machine direction”, MD) thermal shrinkage rate at 150° C. for 1 h of ≤5%, optionally from 0.5% to 4%.
In some embodiments, the separator has a lateral (also referred to as “transverse direction”, TD) thermal shrinkage rate at 150° C. for 1 h of ≤5%, optionally from 0.5% to 4%.
The separator of the present application has low thermal shrinkage rate in both the lateral direction and the longitudinal direction, which can further improve the safety performance of the secondary battery.
In some embodiments, the separator has a perforation strength of ≥350 gf, optionally from 370 gf to 450 gf. The separator of the present application has a high perforation strength, which can further improve the safety performance of the secondary battery.
In some embodiments, the separator has a longitudinal tensile strength of ≥2000 kg/cm2, optionally from 2500 kg/m2 to 4500 kg/m2.
In some embodiments, the separator has a lateral tensile strength of ≥2000 kg/m2, optionally from 2500 kg/m2 to 4500 kg/m2.
The separator of the present application has high tensile strength in both the lateral direction and the longitudinal direction, which results in small probability of breakage of the separator when the secondary battery is expanded, thereby further improving the safety performance of the secondary battery.
In some embodiments, the separator has an air permeability of ≤300 s/100 mL, optionally from 100 s/100 mL to 200 s/100 mL. The separator of the present application has high air permeability, which can improve the ion transport characteristics.
In some embodiments, the separator has a porosity of from 30% to 45%, optionally from 32% to 36%. As a result, this can improve the ion transport characteristics of the separator and reduce the self-discharge of the battery.
In some embodiments, the separator has a wetting length of ≥30 mm, optionally from 30 mm to 80 mm.
In some embodiments, the separator has a wetting speed of ≥3 mm/s, optionally from 3 mm/s to 10 mm/s.
The separator of the present application has good electrolyte infiltration characteristics, which can improve the ion transport characteristics and the capacity exertion of the secondary battery.
In this application, the average particle size Dv50 of a material has well-known meaning in the art, and may be measured with known instruments and methods in the art. For example, it can be readily measured according to “Particle Size Analysis-Laser Diffraction Method” of GB/T 19077-2016 using a laser particle size analyzer (for example, Master Size 3000).
In this application, the specific surface area of a material has well-known meaning in the art, and may be measured with known instruments and methods in the art. For example, a method for analyzing and testing specific surface area by nitrogen adsorption is used according to GB/T 19587-2017, and the specific surface area can be calculated by the BET (BrunauerEmmett Teller) method. Optionally, the analyzing and testing specific surface area by nitrogen adsorption may be performd by a Tri-Star Model 3020 specific surface area & porosity analyzer from Micromeritics, USA.
In the present application, the thermal shrinkage, perforation strength, tensile strength, and air permeability of the separator have well-known meanings in the art and can be measured by methods known in the art. For example, they may be tested with reference to GB/T 36363-2018.
In this application, the wetting length and wetting speed of the separator have well-known meanings in the art, and may be measured with known instruments and methods in the art. An exemplary test method is as follows: cutting a separator into a sample with a width of 5 mm and a length of 100 mm, and fixing both ends of the sample and placing horizontally; Taking 0.5 mg of electrolyte and dropping it in the center of the sample, and after the specified time (1 min in this application), taking a photo and measuring the length of electrolyte diffusion, thereby obtaining the wetting length and wetting speed of the separator. In order to ensure the accuracy of the test results, a plurality of samples (for example, from 5 to 10) can be tested, and the test results are obtained by calculating average value. The electrolyte may be prepared by mixing ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) in a volume ratio of 30:50:20 to obtain an organic solvent, and then dissolving a fully dried LiPF6 in the above organic solvent, to prepare an electrolyte with a concentration of 1 mol/L.
The parameters (for example, areal density, thickness, etc.) of coating layer in the above separator are all parameters of coating layer on one side of the porous substrate.
When the coating layer is disposed on both sides of the porous substrate, if the coating parameters on either side satisfy the requirements in the present application, the separator is considered to fall within the scope of protection of the present application.
A second aspect of embodiments of the present application provides a method for preparing the separator according to the first aspect of embodiments of the present application, comprising the following steps: S1, providing a porous substrate; S2, formulating a coating slurry: mixing nanocellulose and a filler in a predetermined proportion in a solvent to prepare the coating slurry; S3, coating: coating one or more surface of the porous substrate with the coating slurry to form a coating layer, and drying to obtain a separator, wherein the separator comprises a porous substrate and a coating layer disposed on one or more surface of the porous substrate, wherein the coating layer comprises nanocellulose and a filler, and the separator has a moisture content of A ppm, the coating layer has a thickness of H μm, and the separator satisfies 250≤A/H≤1500.
In some embodiments, in S2, the solvent may be water, such as deionized water.
In some embodiments, in S2, the coating slurry may further comprise other components, for example, may further comprise a dispersing agent, a wetting agent, a binder, and the like.
In some embodiments, in S2, the solid content of the coating slurry may be controlled between 28% and 45%, for example, may be between 30% and 38%. When the solid content of the coating slurry is within the above range, the film surface problem of the coating layer and the probability of occurrence of coating unevenness can be effectively reduced, thereby further improving the energy density and safety performance of the secondary battery.
In some embodiments, the above nanocellulose can be obtained as follows: S21, providing a cellulose powder having a whiteness of ≥80%; S22, mixing and reacting the obtained cellulose powder with a modification solution, washing and removing impurities to obtain cellulose nanowhiskers; S23, adjusting the pH of the obtained cellulose nanowhiskers to neutral (e.g., pH of from 6.5 to 7.5), and grinding and cutting to obtain nanocellulose.
Optionally, in S21, the above cellulose powder having a whiteness of ≥80% can be obtained commercially, or can be obtained by a chemical method (e.g., acid hydrolysis method, alkali treatment method, Tempo catalytic oxidation method), a biological method (e.g., enzymatic treatment method), a mechanical method (e.g., ultrafine grinding, ultrasonic crushing, high-pressure homogenization), or the like. The fiber raw material for preparing the above cellulose powder having a whiteness of ≥80% may include one or more of plant fibers such as cotton fibers (e.g. Gossypium fibers, kapok fibers), hemp fibers (e.g. sisal fibers, ramie fibers, jute fibers, flax fibers, marihuana fibers, abaca fibers, etc.), brown fibers, wood fibers, bamboo fibers, and grass fibers.
In some embodiments, the above-mentioned cellulose powder having a whiteness of ≥80% can also be prepared by: loosening the fiber raw material and slag removal, cooking with an alkaline solution (e.g. aqueous NaOH solution, which may have a concentration of 4 wt. % to 20 wt. %, optionally 5 wt. % to 15 wt. %), and then sequentially subjecting to water washing to remove impurities (e.g., water washing for 3 times to 6 times), bleaching (using for example sodium hypochlorite and/or hydrogen peroxide), acid washing to remove impurities, water washing to remove impurities, water discharging, and air drying, to obtain the cellulose powder.
In some embodiments, in S22, the modification solution may be an acid solution (e.g., an aqueous sulfuric acid solution, an aqueous boric acid solution, an aqueous phosphoric acid solution, an aqueous acetic acid solution) or an alkaline solution (for example a urea solution in organic solvent). Optionally, the modification solution is an acid solution.
Optionally, the acid solution may have a concentration of 5 wt. % to 80 wt. %. When an aqueous sulfuric acid solution is used as the modification solution, the concentration of the acid solution may be 40 wt. % to 80 wt. %, thus nanocellulose having a sulfonic acid group can be obtained. When an aqueous boric acid solution is used as the modification solution, the concentration of the acid solution may be 5 wt. % to 10 wt. %, thus nanocellulose having a boric acid group can be obtained. When an aqueous phosphoric acid solution is used as the modification solution, the concentration of the acid solution may be 45 wt. % to 75 wt. %, thus nanocellulose having a phosphoric acid group can be obtained. When an aqueous acetic acid solution is used as the modification solution, the concentration of the acid solution may be 40 wt. % to 80 wt. %, thus nanocellulose having a carboxylic acid group can be obtained.
Optionally, the urea solution in organic solvent is a urea solution in xylene, whereby nanocellulose having an amine group can be obtained.
In some embodiments, in S22, optionally, the mass ratio of the cellulose powder to the modification solution may be from 1:2.5 to 1:50, optionally from 1:5 to 1:30.
When an aqueous sulfuric acid solution is used as the modification solution, the mass ratio of the cellulose powder to the acid solution may be from 1:5 to 1:30. When an aqueous boric acid solution is used as the modification solution, the mass ratio of the cellulose powder to the acid solution may be from 1:20 to 1:50. When an aqueous phosphoric acid solution is used as the modification solution, the mass ratio of the cellulose powder to the acid solution may be from 1:5 to 1:30. When an aqueous acetic acid solution is used as the modification solution, the mass ratio of the cellulose powder to the acid solution may be from 1:5 to 1:30. When a urea solution in organic solvent is used as the modification solution, the mass ratio of the cellulose powder to the urea solution in organic solvent may be from 1:4 to 1:40.
In some embodiments, in S22, when the modification solution is an acid solution, the reaction may be carried out at a condition of not higher than 80° C., optionally at a condition of from 30° C. to 60° C., and the reaction time between the cellulose powder and the modification solution may be from 0.5 h to 4 h, optionally from 1 h to 3 h.
In some embodiments, in S22, when the modification solution is an alkaline solution, the reaction may be carried out under conditions of from 100° C. to 145° C., and the reaction time of the cellulose powder and the modification solution may be from 1 h to 5 h.
In some embodiments, in S23, a grinder may be used for grinding, and a high pressure homogenizer may be used for cutting. By adjusting the grinding parameters of the grinder (e.g. number of grinding, grinding time, etc.) as well as the cutting parameters of the high-pressure homogenizer, nanocelluloses with different average diameters and/or different average lengths can be obtained.
In some embodiments, in S3, a coating machine is adopted in the coating step. In the present application, there is no particular limitation on the type of the coating machine, and for example, a commercially available coating machine can be used. Optionally, the coating machine comprises a gravure roll for transferring the coating slurry onto the porous substrate. Optionally, the number of lines in the gravure roll is from 100 LPI to 300 LPI, more optionally from 125 LPI to 190 LPI.
In some embodiments, in S3, transfer coating, spin spraying, dip coating, or the like may be adopted for the way of coating.
In some embodiments, in S3, a coating speed may be from 30 m/min to 120 m/min, for example from 60 m/min to 90 m/min. When the coating speed is within the above ranges, the film surface problem of the coating layer and the probability of occurrence of coating unevenness can be effectively reduced, thereby further improving the energy density and safety performance of the secondary battery.
In some embodiments, in S3, a linear speed ratio for the coating may be from 0.8 to 2.5, for example may be from 0.8 to 1.5, or from 1.0 to 1.5.
In some embodiments, in S3, a drying temperature may be from 40° C. to 70° C., for example may be from 50° C. to 60° C.
In some embodiments, in S3, drying time may be from 10 seconds to 120 seconds, for example may be from 20 seconds to 80 seconds, or from 20 seconds to 40 seconds.
By controlling the above-mentioned process parameters within the given ranges, the performance of the separator of the present application can be further improved. Those skilled in the art can selectively control one or more of the above-mentioned process parameters according to the actual production situation.
In some embodiments, the method further comprises the step of: S4, secondary coating: coating at least part of surface of the coating layer with a slurry containing a granular binder, and drying to form an adhesive layer.
The preparation method of the separator of the present application can provide a coating layer through one coating process, which greatly simplifies the production process of the separator.
Some raw materials and parameters such as their amounts used in the method for preparing the separator of the present application can be determined with respect to the separator of the first aspect of the embodiments of the present application, and will not be repeatedly described herein. Unless otherwise specified, all raw materials used in the method for preparing the separator of the present application may be commercially available.
The third aspect of embodiments of the present application provides a secondary battery.
Secondary batteries, also known as rechargeable batteries or storage batteries, refer to batteries that can be used continuously by activating active materials through charging after the battery is discharged. Normally, a secondary battery comprises an electrode assembly and an electrolyte, and the electrode assembly comprises a positive electrode plate, a negative electrode plate and a separator, the separator is disposed between the positive electrode plate and the negative electrode plate and is mainly used to prevent short circuit between positive electrode and negative electrode and meanwhile allows active ions to pass through.
The present application has no particular limitation on the type of the secondary battery. For example, the secondary battery may be a lithium ion battery, a sodium ion battery, and the like. In particular, the secondary battery may be a lithium ion secondary battery.
The secondary battery of the third aspect of embodiments of the present application comprises the separator of the first aspect of embodiments of the present application or the separator prepared by the method of the second aspect of embodiments of the present application, wherein the separator is spaced between the positive electrode plate and the negative electrode plate. Optionally, the coating layer according to the first aspect of embodiments of the present application is present on at least the side of the separator close to the negative electrode plate. As a result, the secondary battery of the present application can have the combined characteristics of high energy density, high thermal safety performance and long service life.
In some embodiments, the positive electrode plate comprises a positive electrode current collector and a positive electrode film layer which is disposed on one or more surface of the positive electrode current collector and comprises a positive electrode active material. For example, the positive current collector has two opposite surfaces along the thickness direction of the positive current collector, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive current collector.
When the secondary battery of the present application is a lithium ion battery, the positive electrode active material may comprise, but is not limited to, one or more of lithium transition metal oxides, lithium-containing phosphates, and their respective modified compounds thereof. Examples of lithium transition metal oxides may include, but are not limited to, one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and respective modified compounds thereof. Examples of lithium-containing phosphates may include, but are not limited to, one or more of lithium iron phosphate, composite of lithium iron phosphate with carbon, lithium manganese phosphate, composite of lithium manganese phosphate with carbon, lithium manganese iron phosphate, composite of lithium manganese iron phosphate with carbon, and respective modified compounds thereof.
In some embodiments, in order to further increase the energy density of the secondary battery, the positive electrode active material for the lithium-ion battery may comprise one or more of lithium transition metal oxides having general formula LiaNibCocMdOeAf and modified compounds thereof. 0.8≤a≤1.2, 0.5≤b<1, 0<c<1, 0<d<1, 1≤e≤2, 0≤f≤1, M is selected from one or more of Mn, Al, Zr, Zn, Cu, Cr, Mg, Fe, V, Ti and B, and A s selected from one or more of N, F, S and Cl.
As an example, positive electrode active materials for lithium-ion batteries may include one or more of LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi1/3Co1/3Mn1/3O2 (NCM333), LiNi0.5Co0.2Mn0.3O2 (NCM523), LiNi0.6Co0.2Mn0.2O2 (NCM622), LiNi0.8Co0.1Mn0.1O2 (NCM811), LiNi0.85Co0.15Al0.05O2, LiFePO4 and LiMnPO4.
When the secondary battery of the present application is a sodium ion battery, the positive electrode active material may include but not limited to one or more of sodium-containing transition metal oxides, polyanion materials (such as phosphate, fluorophosphate, pyrophosphate, sulfate, and the like salts), and Prussian blue materials.
As an example, a positive electrode active material for a sodium-ion battery may include one or more of NaFeO2, NaCoO2, NaCrO2, NaMnO2, NaNiO2, NaNi1/2Ti1/2O02, NaNi1/2Mn1/2O2, Na2/3Fe1/3Mn2/3O2, NaNi1/3Co1/3Mn1/3O2, NaFePO4, NaMnPO4, NaCoPO4, Prussian blue materials and the materials having the general formula XpM′q(PO4)rOxY3-x. In general formula XpM′q(PO4)rOxY3-x, 0<p≤4, 0<q≤2, 1≤r≤3, 0≤x≤2, X is selected from one or more of H+, Li+, Na+, K+ and NH4+, M′ is a transition metal cation and optionally is one or more of V, Ti, Mn, Fc, Co, Ni, Cu and Zn, and Y is a halogen anion and optionally is one or more of F, Cl and Br.
In the present application, the modified compounds of the above positive electrode active materials may be doping-modified and/or surface coating-modified compounds of the positive electrode active materials.
In some embodiments, the positive electrode film layer may also optionally comprise a conductive agent for positive electrode. The present application does not particularly limit the type of conductive agent for positive electrode, and as an example, the conductive agent for positive electrode includes one or more of superconducting carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. In some embodiments, the mass content of the conductive agent for positive electrode is ≤5%, based on the total mass of the positive electrode film layer.
In some embodiments, the positive electrode film layer may further optionally comprise a binder for positive electrode. The present application does not particularly limit the type of the binder for positive electrode, and as an example, the binder for positive electrode may include one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorinated acrylate resins. In some embodiments, the mass content of the binder for positive electrode is ≤5%, based on the total mass of the positive electrode film layer.
In some embodiments, the positive electrode current collector may be a metal foil or a composite current collector. As an example of the metal foil, aluminum foil may be used. The composite current collector may include a base layer of polymeric material and a layer of metallic material formed on one or more surface of the base layer of polymeric material. As an example, the metal material may comprise one or more of aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. As an example, the base layer of polymeric material may comprise one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), and the like.
The positive electrode film layer is usually formed by applying a positive electrode slurry on a positive electrode current collector, drying and cold-pressing. The positive electrode slurry is usually formed by dispersing positive electrode active material, an optional conductive agent, an optional binder and any other components in a solvent and stirring them uniformly. The solvent may be N-methylpyrrolidone (NMP), but is not limited thereto.
In some embodiments, the negative electrode plate comprises a negative positive electrode current collector and a negative electrode film layer which is disposed on one or more surface of the negative electrode current collector and comprises a negative electrode active material. For example, the negative current collector has two opposite surfaces along the thickness direction of the negative current collector, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the negative current collector.
The negative electrode active material can be a negative electrode active material well known in the art for secondary batteries. As an example, the negative electrode active material may include but not limited to one or more of natural graphite, artificial graphite, soft carbon, hard carbon, silicon-based material, tin-based material, and lithium titanate. The silicon-based material may include one or more of elemental silicon, silicon oxide, silicon-carbon composite, silicon-nitrogen composite, and silicon alloy. The tin-based material may include one or more of elemental tin, tin oxide, and tin alloy materials.
In some embodiments, the negative electrode film layer may also optionally comprise a conductive agent for negative electrode. The present application does not particularly limit the type of conductive agent for negative electrode, and as an example, the conductive agent for negative electrode may include one or more of superconducting carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. In some embodiments, the mass content of the conductive agent for negative electrode is ≤5%, based on the total mass of the negative electrode film layer.
In some embodiments, the negative electrode film layer may further optionally comprises a binder for negative electrode. The present application does not particularly limit the type of the binder for negative electrode, and as an example, the binder for negative electrode may include one or more of styrene-butadiene rubber (SBR), water-soluble unsaturated resin SR-1B, aqueous acrylic resins (e.g., polyacrylic acid PAA, polymethacrylic acid PMAA, sodium polyacrylate PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), and carboxymethyl chitosan (CMCS). In some embodiments, the mass content of the binder for negative electrode is ≤5%, based on the total mass of the negative electrode film layer.
In some embodiments, the negative electrode film layer may further optionally comprises other auxiliary agents. As examples, other auxiliary agents may include thickeners, e.g., sodium carboxymethylcellulose (CMC), PTC thermistor material, etc. In some embodiments, the mass content of the other auxiliary agents is ≤2%, based on the total mass of the negative electrode film layer.
In some embodiments, the negative electrode collector may be a metal foil or a composite collector. As an example of a metal foil, a copper foil may be used. The composite current collector may include a base layer of polymeric material and a layer of metallic material formed on one or more surface of the base layer of polymeric material. As an example, the metal material may comprise one or more of copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. As an example, the base layer of polymeric material may comprise one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), and the like.
The negative electrode film layer is usually formed by applying a negative electrode slurry on a negative electrode collector, drying and cold-pressing. The negative electrode slurry is typically formed by dispersing the negative active material, optional conductive agent, optional binder, other optional auxiliary agents in a solvent and stirring well. The solvent may be N-methylpyrrolidone (NMP) or deionized water, but is not limited thereto.
The negative electrode plate does not exclude additional functional layers other than the negative electrode film layer. For example, in some embodiments, the negative electrode plate described in the present application further comprises a conductive primer layer (such as composed of a conductive agent and a binder) sandwiched between the negative electrode current collector and the negative electrode film layer, and disposed on the surface of the negative electrode current collector. In some other embodiments, the negative electrode plate described in this application further comprises a protective layer covering the surface of the negative electrode film layer.
During the charging and discharging process of the battery, active ions are intercalated and deintercalated back and forth between the positive electrode plate and the negative electrode plate, and the electrolyte (or electrolytic solution) functions as conducting active ions between the positive electrode plate and the negative electrode plate. There is no specific limitation on the type of electrolyte in the present application, and it can be selected according to actual needs.
The electrolyte includes an electrolyte salt and a solvent. There is no specific limitation on the type of solvent and the electrolyte salt, and they can be selected according to actual needs.
When the secondary battery of the present application is a lithium ion battery, as an example, the electrolyte salt may comprise one or more of lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium difluorosulfimide (LiFSI), lithium bistrifluoromethanesulfonimide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluoro(oxalate)borate (LiDFOB), bis(oxalate)borate (LiBOB), lithium difluorophosphate (LiPO2F2), lithium difluorobisoxalate phosphate (LiDFOP), and lithium tetrafluorooxalate phosphate (LiTFOP).
When the secondary battery of the present application is a sodium ion battery, as an example, the electrolyte salt may comprise, but is not limited to, one or more of sodium hexafluorophosphate (NaPF6), sodium tetrafluoroborate (NaBF4), sodium perchlorate (NaClO4), sodium hexafluoroarsenate (NaAsF6), sodium bisfluorosulfonimide (NaFSI), sodium bistrifluoromethanesulfonimide (NaTFSI), sodium trifluoromethanesulfonate (NaTFS), sodium difluoro(oxalate)borate (NaDFOB), sodium bis(oxalate)borate (NaBOB), sodium difluorophosphate (NaPO2F2), sodium difluorobisoxalate phosphate (NaDFOP) and sodium tetrafluorooxalate phosphate (NaTFOP).
As an example, the solvent may comprise, but is not limited to, one or more of ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl 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), dimethylsulfone (MSM), methylethylsulfone (EMS), and diethylsulfone (ESE).
In some embodiments, the electrolytic solution may optionally comprise an additive. For example, the additives may comprise negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performance of the battery, such as additives that improve overcharging performance of the battery, additives that improve high-temperature performance of the battery, and additives that improve low-temperature power/rating performance of the battery.
In some embodiments, the positive electrode plate, the separator, and the negative electrode plate may be fabricated into an electrode assembly by a winding process and/or a lamination process.
In some embodiments, the secondary battery may comprise an outer packaging. The outer packaging may be used to encapsulate the electrode assembly and the electrolyte.
In some embodiments, the outer packaging of the secondary battery may be a hard housing, such as a hard plastic housing, aluminum housing, steel housing, or the like. The outer packaging of the secondary battery may also be a soft pack, such as a pouch type soft pack. The material of the soft pack may be plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT), and polybutylene succinate (PBS).
The present application does not have particular limitation on the shape of the secondary battery, which may be cylindrical, square, or other arbitrary shapes.
In some embodiments, referring to
The preparation method of the secondary battery of the present application is well known. In some embodiments, a positive electrode plate, a separator, a negative electrode plate, and electrolytic solution can be assembled to form a secondary battery. As an example, the positive electrode plate, the separator, and the negative electrode plate can be formed into an electrode assembly by a winding process and/or a laminating process; the electrode assembly is placed in an outer packaging and dried, followed by injection with the electrolyte; after the processes including vacuum encapsulation, steady standing, chemical formation, and shaping, a secondary battery is obtained.
In some embodiments, the secondary battery of the present application can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
Optionally, the battery module 4 may further include a housing having an accommodating space in which a plurality of secondary batteries 5 are accommodated.
In some embodiments, the above-mentioned battery module may also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
The fourth aspect of embodiments of the present application provides an electrical device comprising one or more of the secondary battery, battery module, and battery pack of the present application. The secondary battery, battery module or battery pack can be used as a power source of the electrical device, and can also be used as an energy storage unit of the electrical device. The electrical device may be, but is not limited to, 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 vehicle, an electric truck), an electric train, a ship, a satellite, an energy storage system, etc.
The electrical device may comprise the secondary battery, the battery module or the battery pack selected according to its usage requirements.
As another example, the electrical device may be a mobile phone, a tablet computer, a notebook computer, etc. The electric device is generally required to be light and thin, and a secondary battery can be used as a power source.
The following examples are intended to describe the present application more specifically, merely for the purpose of illustration. Various modifications and variations within the scope of the present application are apparent to those skilled in the related art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on mass, and all reagents used in the examples are commercially available or synthesized by conventional methods, and can be directly obtained without further treatment, and the instruments used in the examples are commercially available.
After loosening the Gossypium linter and slag removal by a cotton opener, the obtained mixture was cooked at 150° C. with 5 wt. % NaOH aqueous solution for 2 hours, and then washed with water to remove impurities (3 times of water washing), bleached with sodium hypochlorite, washed with diluted hydrochloric acid to remove impurities, washed with water to remove impurities (1 time of water washing), water discharged and dried with air flow to obtain Gossypium cellulose powder with whiteness of ≥85%.
1 kg of the obtained Gossypium cellulose powder was mixed with 30 kg of 60 wt. % sulfuric acid aqueous solution, and the reaction was carried out at 60° C. for 1.5 h. After the reaction was completed, by washing with water (3 times of water washing), filtering, and removing acid and impurities, the cellulose nanowhiskers with sulfonic acid modifying groups were obtained.
The pH of cellulose nanowhiskers with sulfonic acid modifying groups was adjusted to neutral with 10 wt. % aqueous NaOH solution, and then dispersed with a grinder at high speed for 2.5 h. The grinding were carried out for 2 times, and then a high pressure homogenizer was used for nanoscale cutting, to obtain the nanocellulose C1 with sulfonic acid modifying groups having an average length of 425 nm and an average diameter of 25 nm, and the molar ratio of sulfonic acid groups to hydroxyl groups of 5:3.
Nanocellulose C2 to nanocellulose C10 were prepared in a similar manner to nanocellulose C1, with the differences detailed in Table 1.
After loosening the Gossypium linter and slag removal by a cotton opener, the obtained mixture was cooked at 150° C. with 5 wt. % NaOH aqueous solution for 2 hours, and then washed with water to remove impurities (3 times of water washing), bleached with sodium hypochlorite, washed with diluted hydrochloric acid to remove impurities, washed with water to remove impurities (1 time of water washing), water discharged and dried with air flow to obtain Gossypium cellulose powder with whiteness of ≥85%. The obtained Gossypium cellulose powder was mixed with 20 wt. % aqueous NaOH solution at 10° C., stirred for 2 h, filtered, and washed with water twice to obtain alkali cellulose powder.
50 g of the obtained alkali cellulose powder and 200 g of urea were placed in a three-port reactor with an oil-water separator. After the urea was dissolved, 5 g of xylene was added, and the temperature was raised to 137° C. under stirring. The reaction was terminated after 4 hours, followed by water washing (3 times of water washing), filtering and drying, to obtain cellulose carbamate.
The obtained cellulose carbamate was dissolved in 5 wt % aqueous NaOH solution to obtain a homogeneous cellulose carbamate solution; and the cellulose carbamate solution was then dispersed with a grinder at high speed for 2.5 h. The grinding were carried out for 2 times, and then a high pressure homogenizer was used for nanoscale cutting, to obtain the nanocellulose with amine modifying groups having an average length of 425 nm and an average diameter of 25 nm, and the molar ratio of amine groups to hydroxyl groups of 4:3.
The molar ratio of modifying groups to hydroxyl groups can be measured by the following method: according to the phthalic anhydride method in GB/T 12008.3-2009, the hydroxyl values of raw material cellulose and modified nanocellulose (milligrams of potassium hydroxide equivalent to the hydroxyl content per gram of sample) were respectively tested, and the obtained numerical unit was mg KOH/g, which was converted into mmol/g as the hydroxyl content. The content of the modifying group (i.e. the content of the modified hydroxyl group) can be obtained by subtracting the hydroxyl content of the modified nanocellulose from the hydroxyl content of raw material cellulose, and thus the molar ratio of the modifying group to the hydroxyl group can be calculated.
Unmodified nanocellulose with a product model of CNWS-50 purchased from Zhongke Leiming (Beijing) Technology Co., Ltd. was used, and can be further processed using a grinder and/or a high-pressure homogenizer to obtain nanocellulose with different average diameters and/or different average lengths. See Table 1 for details.
(1) Preparation of separator
S1, providing a PE porous substrate: having thickness of 4.8 μm and porosity of 39%.
S2, formulating a coating slurry: mixing evenly the above prepared nanocellulose C1, alumina (with secondary particle morphology, average particle size Dv50 of 140 nm, BET specific surface area of 30 m2/g) as a filler, and an aqueous solution type polyacrylic acid as a binder at a mass ratio of 20:79.1:0.9 in an appropriate amount of deionized water as solvent to obtain a coating slurry with a solid content of 35 wt. %.
S3, coating: coating both surfaces of the PE porous substrate with the formulated coating slurry using a coating machine, and a separator was obtained by drying and slitting steps. The coating layer on one side of PE porous substrate had an areal density of 1.1 g/m2 and a thickness of 0.8 μm. The coating machine included a gravure roll, and the number of lines in the gravure roll of 175 LPI, a coating speed of 90 m/min, a coating linear speed ratio of 1.2, a drying temperature of 55±5° C., and a drying time of 50 seconds.
The positive electrode active material LiNi0.8Co0.1Mn0.1O2 (NCM811), carbon black (Super P) as conductive agent, and polyvinylidene fluoride (PVDF) as binder were uniformly mixed at a mass ratio of 96.2:2.7:1.1 in an appropriate amount of solvent N-methylpyrrolidone (NMP) to obtain a positive electrode slurry; the positive electrode slurry was applied on an aluminum foil as positive electrode collector, and then dried and cold-pressed, slitted, and cut, to give the positive electrode plate. The positive electrode plate had an areal density of 0.207 mg/mm2 and a compacted density of 3.5 g/cm3.
Artificial graphite as negative electrode active material, carbon black (Super P) as conductive agent, styrene butadiene rubber (SBR) as binder, and carboxymethyl cellulose sodium (CMC) were mixed at a mass ratio of 96.4:0.7:1.8:1.1 in a suitable solvent deionized water to obtain a negative electrode slurry; the negative electrode slurry was applied onto a copper foil as negative electrode current collector; and after processes including drying, cold-pressing, slitting and cutting, the negative electrode plate was obtained. The negative electrode plate had an areal density of 0.126 mg/mm2 and a compacted density of 1.7 g/cm3.
Ethylene carbonate (EC) and ethyl methyl carbonate (EMC) at a volume ratio of 30:70 were mixed to obtain an organic solvent, and then a fully dried LiPF6 was dissolved in the above organic solvent, to prepare an electrolyte with a concentration of 1 mol/L.
The positive electrode plate, the separator, and the negative electrode plate were stacked and wound in sequence to obtain an electrode assembly; the electrode assembly was placed in a outer packaging and dried, followed by injection with the electrolyte; after the processes including vacuum encapsulation, standing, chemical formation, and shaping, a secondary battery was obtained.
The secondary batteries were prepared by a method similar to that of Example 1, except that the amounts of nanocellulose C1 and filler added in the preparation of the separators were different, and the specific parameters were detailed in Table 2.
The secondary batteries were prepared by a method similar to that of Example 1, except that the types of nanocellulose used in the preparation of the separators were different, and the specific parameters were detailed in Tables 1 and 2.
The secondary batteries were prepared by a method similar to that of Example 1, except that the specific surface areas of alumina as the filler used in the preparation of the separator were different, and the specific parameters were detailed in Table 2.
The alumina with secondary particle morphology used as the filler in Example 18 had an average particle size Dv50 of 350 nm and a BET specific surface area of 15 m2/g. The alumina with secondary particle morphology used as the filler in Example 19 had an average particle size Dv50 of 175 nm and a BET specific surface area of 20 m2/g. The alumina with secondary particle morphology used as the filler in Example 20 had an average particle size Dv50 of 113 nm and a BET specific surface area of 35 m2/g. The alumina with secondary particle morphology used as the filler in Example 21 had an average particle size Dv50 of 85 nm and a BET specific surface area of 40 m2/g.
The secondary batteries were prepared by a method similar to that of Example 1, except that the areal densities of the coating layers in the preparation of the separators were different, and the specific parameters were detailed in Table 2.
The secondary batteries were prepared by a method similar to that of Example 1, except that alumina with a secondary particle morphology (having an average particle size Dv50 of 140 nm and a BET specific surface area of 30 m2/g) and alumina with primary particle morphology (having an average particle size Dv50 of 600 nm and a BET specific surface area of 7 m2/g) were used as the filler, and the specific amounts were detailed in Table 2.
The secondary batteries were prepared by a method similar to that of Example 1, except that the types of nanocellulose used in the preparation of the separators were different, and the fillers used were all alumina with primary particle morphology (having an average particle size of 1000 nm and BET specific surface area of 5 m2/g), and the specific parameters were detailed in Tables 1 and 2.
An empty dish was placed in a drying oven and heated at 45° C. for 8 h. and then cooled in a desiccator for 1 h. 0.08 g to 0.1 g of the separator sample was weighed and placed in the cooled empty dish, then the empty dish was placed in a moisture tester and heated at 170° C. for 10 minutes to test the moisture content of the separator. Test methods: The test method may be Karl Fischer moisture testing method, and the test instrument may be Metrohm 831 Karl Fischer moisture tester.
Sample preparation: The separator prepared above was punched into samples with a width of 50 mm and a length of 100 mm using a punching machine; and five parallel samples were placed on A4 paper and fixed; and then the A4 paper loaded with the samples was placed on corrugated paper with a thickness of from 1 mm to 5 mm.
Sample test: a blast oven was set to the temperature of 150° C.; After the temperature reached the set temperature and stabilized for 30 minutes, the A4 paper placed on the corrugated paper was placed into the blast oven, following by starting timing until the set time (1 h in this application) was reached; the length and width of the separator were measured, and the values were marked as a and b, respectively.
Calculation of thermal shrinkage rate: machine direction (MD) heat shrinkage rate=[(100−a)/100]×100%, transverse direction (TD) thermal shrinkage rate=[(50−b)/50]×100%, and the average value of five parallel samples was taken as the test result.
Time required for 100 mL of air to pass through the separator at 25° C. was tested, and the average value of 5 parallel samples was taken as the test result. The test instrument may be the Kumagai KRK Wangyan air permeability tester.
At 25° C., the secondary battery was charged to 4.2 V with a constant current of 1 C, continued to charge at constant voltage until the current was ≤0.05 C, at which time the secondary battery was in a fully charged state and the charge capacity was recorded, i.e. the charge capacity after the first cycle; After the secondary battery was allowed to stand for 5 min, it was discharged to 2.8 V with a constant current of 1 C, which was a cyclic charge and discharge process and at which time the discharge capacity was recorded, i.e. the discharge capacity after the first cycle. The secondary battery was subjected to the above cyclic charge-discharge process, and the discharge capacity after each cycle was recorded. Capacity retention ratio (%) of secondary battery at 25° C. after 500 cycles=discharge capacity after 500 cycles/discharge capacity after the first cycle×100%.
At 25° C., the secondary battery was charged to 4.2 V with a constant current of 1 C, and continued to charge at constant voltage until the current was ≤0.05 C; after standing for 5 min, the secondary battery was discharged to 2.8 V with a constant current of 1 C, and the discharge capacity at this time, i.e. the capacity before storage, was recorded. At 25° C., the secondary battery was charged to 4.2 V with a constant current of 1 C, continued to charge at constant voltage until the current was ≤0.05 C, at which time the secondary battery was in a fully charged state; then the secondary battery was placed in a constant temperature oven at 60° C., stored for 30 days, and then taken out of the constant temperature oven; then the secondary battery was discharged to 2.8 V with a constant current of 1 C, at which time the discharge capacity was recorded, i.e. the capacity after the storage. Capacity retention ratio (%) of secondary battery after storage at 60° C. for 30 days=the capacity after storage/the capacity before storage×100%.
The secondary battery was charged with a constant current of 1 C to 4.2 V at 25° C., and continued to charge with the constant voltage until the current was ≤0.05 C, and allowed to stand for 5 minutes; then secondary battery with a fixture was tested in a DHG-9070A DHG series high-temperature oven, and raised from room temperature to 80±2° C. at a rate of 5° C./min, and held for 30 minutes; then, the temperature was raised at a heating rate of 5° C./min. Every time the temperature was raised by 5° C., the temperature was kept for 30 minutes until the secondary battery failed. During the temperature rise process, the surface temperature change of the secondary battery was monitored. When the temperature starts to rise sharply, the corresponding oven temperature was recorded as the hot box failure temperature of the secondary battery. The higher hot box failure temperature of a secondary battery means the better thermal safety performance of the secondary battery.
As can be seen from Table 3, by providing a coating layer comprising nanocellulose and filler on both surfaces of the porous substrate of the separator, and controlling the ratio of the moisture content of the separator to the thickness of the coating layer to satisfy 250≤A/H≤1500, it enables the thinned separator to have high heat resistance and high air permeability while having low moisture content, and further enables the secondary battery to have high thermal safety performance and long service life and to have the hot box failure temperature of 150° C. or more, and the capacity retention ratio of 88% or more after 500 cycles at 25° C. and the capacity retention ratio of 84% or more after 30 days of storage at 60° C.
It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and within the scope of the technical solutions of the present application, embodiments that have substantially the same configuration as the technical idea and exert the same effects are included in the technical scope of the present application. In addition, without departing from the scope of the present application, various modifications conceivable by those skilled in the art can be introduced to the embodiments, and other forms constructed by combining some components in the embodiments are also included in the scope of the present application.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/101261 | Jun 2022 | WO | international |
This application is a Continuation of International Application No. PCT/CN2022/112589 filed on Aug. 15, 2022, which claims priority to PCT Patent application PCT/CN2022/101261 filed on Jun. 24, 2022, both of which are incorporated herein by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2022/112589 | Aug 2022 | WO |
| Child | 18991721 | US |
