CN113013551B - Water-based nano composite modified material for lithium battery diaphragm, preparation method of water-based nano composite modified material and light-weight lithium battery diaphragm - Google Patents
Water-based nano composite modified material for lithium battery diaphragm, preparation method of water-based nano composite modified material and light-weight lithium battery diaphragm Download PDFInfo
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- CN113013551B CN113013551B CN202110121280.1A CN202110121280A CN113013551B CN 113013551 B CN113013551 B CN 113013551B CN 202110121280 A CN202110121280 A CN 202110121280A CN 113013551 B CN113013551 B CN 113013551B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a water-based nano composite modified material for a lithium battery diaphragm, a preparation method thereof and a light-weight lithium battery diaphragm, wherein the modified material takes water as a liquid-phase component, and also comprises a solid-phase component, wherein the solid-phase component comprises nano cellulose and a natural shell material; the mass fraction of the nanocellulose and the natural shell material in the modified material is 0.1-15%, and the mass fraction of the nanocellulose in the solid phase component is 4-40%. According to the invention, the nano-cellulose and the natural shell material with specific proportion and concentration are dispersed in water to form the modified material, and the modified material is used for modifying the diaphragm base material, so that the battery diaphragm with excellent electrolyte wettability, ion mobility, ion conductivity, thermal stability, air permeability and peel strength can be obtained, the diaphragm is suitable in thickness and small in surface density, the light lithium ion battery diaphragm is beneficial to obtaining, and the performance of the lithium ion battery is further improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an aqueous nano composite modified material for a lithium battery diaphragm, a preparation method of the aqueous nano composite modified material and a light lithium battery diaphragm.
Background
The lithium ion battery has the advantages of high energy density and long cycle life, and is a potential energy source for electric vehicles and hybrid electric vehicles. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte and the like. The battery diaphragm mainly plays a role in preventing direct contact of positive and negative electrodes, preventing short circuit of the battery and transmitting ions, and although the diaphragm does not directly participate in electrochemical reaction of the battery, the performance of the diaphragm affects the properties of the battery, such as interface structure, internal resistance and the like, so that the performance of the battery, such as energy density, cycle life, multiplying power and the like, is affected. In addition, the thermal stability of the separator also determines the temperature range in which the battery operates and the safety of the battery.
At present, commercial lithium ion battery diaphragms are mainly polyolefin organic diaphragms. Such separators have the advantages of low price, good mechanical properties and better electrochemical stability, but also have disadvantages, such as: the electrolyte has poor wettability, low porosity and poor thermal stability, is easy to shrink or melt at high temperature, and has potential safety hazard.
In order to improve the wettability and the thermal stability of the electrolyte, the common method is to coat inorganic particles on a polymer microporous membrane, and the existence of the inorganic particles can improve the wettability and the high-temperature dimensional stability of the electrolyte of the multilayer composite diaphragm, so that the performance of the lithium ion battery is improved. However, the inorganic particle coating layer has poor adhesion to the polymer separator and is likely to be peeled off. For example, "Cellulose ultrafine fibers embedded with titanium particles as a high performance and eco-friendly separator for lithium-ion batteries, Carbohydrate Polymers 189(2018) 145-151" discloses a technical solution for modifying a polyethylene membrane by combining nano anatase-type titanium dioxide fine particles and Cellulose acetate, although it achieves higher high temperature resistance of the membrane, since the titanium dioxide fine particles are inorganic particles, the titanium dioxide particles and the membrane are easily detached; for example, "Colloidal silica nanoparticles-associated structured control of cellulose and inorganic nanoparticles for lithium-ion batteries," Journal of Power Sources 242(2013)533-540 "discloses a silica-modified nanofiber paper as a lithium ion battery separator, but since the particles used are also inorganic particles, there is also a technical problem of inorganic particle detachment. Because of the problem of easy falling off of inorganic particle coating, other improving methods are proposed by researchers, such as "High strain safety lithium-ion batteries" High strain safety separator from polyethylene/cellulose nanofibers blend, Journal of Power Sources 400(2018)502-510 "which discloses a lithium ion battery diaphragm modified by polyformaldehyde cellulose, which shows higher safety and performance enhancement, can be kept stable at 180 ℃, but the air permeability is reduced by nearly one time, and the surface resistance is larger.
In summary, it is difficult to provide a battery separator having excellent thermal stability, electrolyte wettability, air permeability and peel strength in the prior art.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a water-based nano composite modified material for a lithium battery diaphragm, a preparation method thereof and a light-weight lithium battery diaphragm.
The invention adopts the following technical scheme:
in a first aspect, the invention provides a water-based nano composite modified material for a lithium battery diaphragm, which takes water as a liquid-phase component, and the modified material also comprises a solid-phase component, wherein the solid-phase component comprises nano cellulose and a natural shell material;
the mass fraction of the nanocellulose and the natural shell material in the modified material is 0.1-15%, and the mass fraction of the nanocellulose in the solid phase component is 4-40%.
According to the invention, the nano-cellulose and the natural shell material with specific proportion and concentration are dispersed in water to form the modified material, the modified material is adopted to modify the diaphragm base material, so that the battery diaphragm with excellent electrolyte wettability, ion mobility, ion conductivity, thermal stability, air permeability and peel strength can be obtained, the modified diaphragm is proper in thickness and small in surface density, the light-weight lithium ion battery diaphragm is favorably obtained, and the performances of the battery such as energy density and the like are further improved.
The natural shell material of the present invention is preferably an eggshell and/or a shell, the eggshell including an avian eggshell, a reptile eggshell, etc., and is further preferably one or more of an eggshell, a duck eggshell, and a goose eggshell.
Preferably, the mass fractions of the nanocellulose and the natural shell material in the modified material are 2-15%, and more preferably 6-12%.
Preferably, the mass percentage concentration c of the nanocellulose in the modifying material and the length-diameter ratio L/d of the nanocellulose satisfy: and c is (0.03-0.05) × L/d%, wherein L is the average length of the nanocellulose, and d is the average diameter of the nanocellulose.
After the conditions are met, the obtained modified material can be uniformly and stably dispersed, sedimentation is not easy to occur, the increment of the air permeability and the surface density of the coated diaphragm is small, and the performances of the diaphragm such as heat resistance, stability and the like are improved.
Preferably, the average diameter of the nano-cellulose is 20-50 nm.
Preferably, the natural shell material is in powder form.
Further preferably, the natural shell material has a particle size d' which satisfies the average diameter d of the nanocellulose
According to the invention, the particle size relationship between the nano-cellulose and the natural shell material is further researched, and the finding that when the relationship is satisfied, the bonding strength between the nano-cellulose and the natural shell material and the surface density of the diaphragm can be better considered, so that the natural shell material is prevented from falling off and blocking holes, and the battery diaphragm is prevented from being too heavy to influence the battery performance due to too high surface density.
Preferably, the solid phase component further comprises inorganic particles with the particle size of 180-300 nm, and the inorganic particles account for 1-5 wt% of the natural shell material.
A certain amount of large-particle-size inorganic particles are added into the modified material, so that the roughness of the diaphragm can be increased, and the diaphragm is prevented from slipping in the process of winding and assembling the battery in a matching way with the electrode plate.
Further preferably, the inorganic particles are one or more of alumina, titania, zirconia.
In a second aspect, the invention also provides a preparation method of the aqueous nanocomposite modified material for the lithium battery diaphragm.
The preparation method provided by the invention comprises the step of mixing a first slurry and a second slurry, wherein the first slurry comprises nano cellulose and water, and the second slurry comprises a natural shell material and water.
Preferably, the second slurry further comprises 0.01-0.2 wt% of a binder.
More preferably, the binder is polyvinyl alcohol with alcoholysis degree of 97-99 mol% and viscosity of 25-30 mPa.s.
The invention adopts less or no adhesive, so the invention is not easy to block the gap of the diaphragm, and the obtained diaphragm has excellent air permeability and ionic conductivity.
When the modified material further comprises inorganic particles with the particle size of 180-300 nm, the inorganic particles can be added after the first slurry and the second slurry are uniformly mixed during preparation, and the inorganic particles are stirred until the inorganic particles are uniformly dispersed.
In a third aspect, the invention provides a light-weight lithium battery separator, which comprises a substrate, wherein the substrate is made of a porous membrane material, and a modification layer formed by the aqueous nanocomposite modification material for the lithium battery separator is arranged on at least one surface of the substrate.
Among them, the porous membrane material is preferably a polyethylene porous membrane and/or a polypropylene porous membrane.
The modifying material is attached to the substrate surface in a manner that is not limited to coating. The coating method is a conventional technical means which is known to those skilled in the art, and includes blade coating, dip coating, spray coating, spin coating, and the like. In the specific embodiment of the invention, the modified material is coated on the surface of the base material by adopting a blade coating mode, and the coating speed is preferably 30-80 m/min. And drying the composite diaphragm at 40-90 ℃ after coating.
Preferably, the thickness of the base material is 6 to 20 μm, and more preferably 9 to 13 μm.
Preferably, the thickness of the modification layer is 200-1000 nm.
Preferably, in the process of preparing the composite separator, the substrate is subjected to roughening treatment.
In a preferred embodiment of the present invention, there is provided a light-weight lithium battery separator wherein the modified layer has an areal density of 1.2g/m or less2(currently commercialized Al)2O3The coating thickness is usually 3 μm and the areal density of the coating is > 6g/m2) And has excellent wettability to carbonate electrolytes (for example: contact angle of 1M LiPF6/EC + DMC electrolyte<5 deg.C), and excellent thermal stability (150 deg.C/1 h, shrinkage rate<5%) and resistance to high voltages (electrochemical window > 4.8V).
In a fourth aspect, the invention also provides an application of the light weight lithium battery separator.
A lithium ion battery adopts the light lithium battery diaphragm as a diaphragm. In a specific lithium ion battery, the light lithium battery diaphragm can be cut into a required shape and size according to requirements, and then assembled with a positive electrode, a negative electrode, an electrolyte and the like to form the target lithium ion battery.
The invention provides an aqueous nano composite modified material for a lithium battery diaphragm, which is formed by dispersing nano cellulose and a natural shell material in water at a specific proportion and concentration, and the modified material is used for modifying a diaphragm base material, so that the battery diaphragm with excellent electrolyte wettability, ion mobility, ion conductivity, thermal stability, air permeability and peel strength can be obtained, the diaphragm is suitable in thickness and small in surface density, the light lithium ion battery diaphragm is favorably obtained, and the performance of a lithium ion battery is further improved.
Drawings
Fig. 1 is a diagram of a light weight lithium battery separator provided in embodiment 1 of the present invention;
fig. 2 is a surface topography of a light weight lithium battery separator provided in embodiment 1 of the present invention;
fig. 3 is a cross-sectional view of a light-weight lithium battery separator provided in embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a water-based nano composite modified material for a lithium battery diaphragm, and a preparation method of the water-based nano composite modified material comprises the following steps:
dispersing 160g of nano-cellulose with the diameter of 50nm (d 50-50 nm) and the length of 2 microns in 4kg of deionized water, and stirring and dispersing for later use; dispersing 800g of egg shell powder with the diameter of 30-50nm in 5kg of deionized water, adding 0.1 wt% of polyvinyl alcohol (alcoholysis degree: 99 mol%, viscosity: 28mPa.s), stirring and dispersing for later use; and (3) stirring the nano cellulose pulp and the eggshell pulp at a high speed, homogenizing for 5 hours, adding 40g of 250nm alumina particles, and continuously stirring for 5 hours to obtain the nano cellulose/eggshell slurry.
The present invention also provides a light weight lithium battery separator, which is composed of a polyethylene porous membrane as a substrate and a modification layer attached to both sides of the polyethylene porous membrane, and the preparation method thereof is as follows:
preparing a polyethylene porous membrane with the thickness of 11 mu m, and roughening the polyethylene porous membrane by using a brush;
the prepared modified material is coated on two sides of the porous membrane at a coating rate of 50m/min, and then dried in an oven at 60 ℃ to obtain a diaphragm, namely a sample S1.
Fig. 1 is a physical diagram of a light-weight lithium battery separator provided in this embodiment; FIG. 2 is a surface topography of the light weight lithium battery separator; FIG. 3 is a cross-sectional profile of the light weight lithium battery separator.
Example 2
The embodiment provides a water-based nano composite modified material for a lithium battery diaphragm, and a preparation method of the water-based nano composite modified material comprises the following steps:
dispersing 240g of nano-cellulose with the diameter of 20nm (d50 is 20nm) and the length of 1.2 mu m in 4kg of deionized water, and stirring and dispersing for later use; 745g of egg shell powder with the diameter of 15-20nm is dispersed in 5kg of deionized water, 0.1 wt% of polyvinyl alcohol (alcoholysis degree: 99 mol%, viscosity: 28mPa.s) is added, stirred and dispersed for standby; and (3) stirring the nano cellulose pulp and the eggshell pulp at a high speed, homogenizing for 5 hours, adding 15g of 200nm alumina particles, and continuously stirring for 5 hours to obtain the nano cellulose/eggshell slurry.
The present invention also provides a light weight lithium battery separator, which is composed of a polyethylene porous membrane as a substrate and a modification layer attached to both sides of the polyethylene porous membrane, and the preparation method thereof is as follows:
preparing a polyethylene porous membrane with the thickness of 11 mu m, and roughening the polyethylene porous membrane by using a brush;
the prepared modified material is coated on two sides of the porous membrane at a coating rate of 50m/min, and then dried in an oven at 50 ℃ to obtain a diaphragm, namely a sample S2.
Example 3
The embodiment provides a water-based nano composite modified material for a lithium battery diaphragm, and a preparation method of the water-based nano composite modified material comprises the following steps:
dispersing 240g of nano-cellulose with the diameter of 20nm (d50 is 20nm) and the length of 1.2 mu m in 4kg of deionized water, and stirring and dispersing for later use; 745g of egg shell powder with the diameter of 15-20nm is dispersed in 5kg of deionized water, 0.1 wt% of polyvinyl alcohol (alcoholysis degree: 99 mol%, viscosity: 28mPa.s) is added, stirred and dispersed for standby; and (3) stirring the nano cellulose pulp and the eggshell pulp at a high speed, and homogenizing for 5 hours to obtain the nano cellulose egg yolk.
The present invention also provides a light weight lithium battery separator, which is composed of a polyethylene porous membrane as a substrate and a modification layer attached to both sides of the polyethylene porous membrane, and the preparation method thereof is as follows:
preparing a polyethylene porous membrane with the thickness of 11 mu m, and roughening the polyethylene porous membrane by using a brush;
the prepared modified material is coated on two sides of the porous membrane at a coating rate of 50m/min, and then dried in an oven at 50 ℃ to obtain a diaphragm, namely a sample S3.
Example 4
The embodiment provides a water-based nano composite modified material for a lithium battery diaphragm, and a preparation method of the water-based nano composite modified material comprises the following steps:
dispersing 160g of nano-cellulose with the diameter of 50nm (d 50-50 nm) and the length of 2 microns in 4kg of deionized water, and stirring and dispersing for later use; dispersing 800g of alumina particles with the diameter of 50nm in 5kg of deionized water, adding 0.1 wt% of polyvinyl alcohol (alcoholysis degree: 99 mol%, viscosity: 28mPa.s), stirring and dispersing for later use; and (3) stirring the nano cellulose slurry and the alumina slurry at a high speed, homogenizing for 5 hours, adding 40g of 250nm alumina particles, and continuously stirring for 5 hours to obtain the nano cellulose/alumina composite material.
The present invention also provides a light weight lithium battery separator, which is composed of a polyethylene porous membrane as a substrate and a modification layer attached to both sides of the polyethylene porous membrane, and the preparation method thereof is as follows:
preparing a polyethylene porous membrane with the thickness of 11 mu m, and roughening the polyethylene porous membrane by using a brush;
the prepared modified material is coated on two sides of the porous membrane at a coating rate of 50m/min, and then dried in an oven at 60 ℃ to obtain a diaphragm, namely a sample S4.
Example 5
The embodiment provides a water-based nano composite modified material for a lithium battery diaphragm, and a preparation method of the water-based nano composite modified material comprises the following steps:
160g of alumina particles with the diameter of 50nm are dispersed in 4kg of deionized water, and are stirred and dispersed for standby; dispersing 800g of egg shell powder with the diameter of 30-50nm in 5kg of deionized water, adding 0.1 wt% of polyvinyl alcohol (alcoholysis degree: 99 mol%, viscosity: 28mPa.s), stirring and dispersing for later use; stirring the alumina slurry and the eggshell slurry at a high speed, homogenizing for 5 hours, adding 40g of 250nm alumina particles, and continuously stirring for 5 hours to obtain the composite.
The present invention also provides a light weight lithium battery separator, which is composed of a polyethylene porous membrane as a substrate and a modification layer attached to both sides of the polyethylene porous membrane, and the preparation method thereof is as follows:
preparing a polyethylene porous membrane with the thickness of 11 mu m, and roughening the polyethylene porous membrane by using a brush;
the prepared modified material is coated on two sides of the porous membrane at a coating rate of 50m/min, and then dried in an oven at 60 ℃ to obtain a diaphragm, namely a sample S5.
Example 6
The embodiment provides a water-based nano composite modified material for a lithium battery diaphragm, and a preparation method of the water-based nano composite modified material comprises the following steps:
dispersing 160g of nano-cellulose with the diameter of 50nm (d 50-50 nm) and the length of 2 microns in 4kg of deionized water, and stirring and dispersing for later use; dispersing 800g of 150 nm-diameter egg shell powder in 5kg of deionized water, adding 0.1 wt% of polyvinyl alcohol (alcoholysis degree: 99 mol%, viscosity: 28mPa.s), stirring and dispersing for later use; and (3) stirring the nano cellulose pulp and the eggshell pulp at a high speed, homogenizing for 5 hours, adding 40g of 250nm alumina particles, and continuously stirring for 5 hours to obtain the nano cellulose/eggshell slurry.
The present invention also provides a light weight lithium battery separator, which is composed of a polyethylene porous membrane as a substrate and a modification layer attached to both sides of the polyethylene porous membrane, and the preparation method thereof is as follows:
preparing a polyethylene porous membrane with the thickness of 11 mu m, and roughening the polyethylene porous membrane by using a brush;
the prepared modified material is coated on two sides of the porous membrane at a coating rate of 50m/min, and then dried in an oven at 60 ℃ to obtain a diaphragm, namely a sample S6.
Example 7
The embodiment provides a water-based nano composite modified material for a lithium battery diaphragm, and a preparation method of the water-based nano composite modified material comprises the following steps:
dispersing 160g of nano-cellulose with the diameter of 250nm (d 50-250 nm) and the length of 2 microns in 4kg of deionized water, and stirring and dispersing for later use; dispersing 800g of egg shell powder with the diameter of 30-50nm in 5kg of deionized water, adding 0.1 wt% of polyvinyl alcohol (alcoholysis degree: 99 mol%, viscosity: 28mPa.s), stirring and dispersing for later use; and (3) stirring the nano cellulose pulp and the eggshell pulp at a high speed, homogenizing for 5 hours, adding 40g of 250nm alumina particles, and continuously stirring for 5 hours to obtain the nano cellulose/eggshell slurry.
The present invention also provides a light weight lithium battery separator, which is composed of a polyethylene porous membrane as a substrate and a modification layer attached to both sides of the polyethylene porous membrane, and the preparation method thereof is as follows:
preparing a polyethylene porous membrane with the thickness of 11 mu m, and roughening the polyethylene porous membrane by using a brush;
the prepared modified material is coated on two sides of the porous membrane at a coating rate of 50m/min, and then dried in an oven at 60 ℃ to obtain a diaphragm, namely a sample S7.
Example 8
The embodiment provides a water-based nano composite modified material for a lithium battery diaphragm, and a preparation method of the water-based nano composite modified material comprises the following steps:
dispersing 300g of nano-cellulose with the diameter of 50nm (d50 ═ 50nm) and the length of 2 mu m in 4kg of deionized water, and stirring and dispersing for later use; 650g of egg shell powder with the diameter of 30-50nm is dispersed in 5kg of deionized water, 0.1 wt% of polyvinyl alcohol (alcoholysis degree: 99 mol%, viscosity: 28mPa.s) is added, stirred and dispersed for standby; and (3) stirring the nano cellulose pulp and the eggshell pulp at a high speed, homogenizing for 5 hours, adding 50g of 250nm alumina particles, and continuously stirring for 5 hours to obtain the nano cellulose/eggshell slurry.
The present invention also provides a light weight lithium battery separator, which is composed of a polyethylene porous membrane as a substrate and a modification layer attached to both sides of the polyethylene porous membrane, and the preparation method thereof is as follows:
preparing a polyethylene porous membrane with the thickness of 11 mu m, and roughening the polyethylene porous membrane by using a brush;
the prepared modified material is coated on two sides of the porous membrane at a coating rate of 50m/min, and then dried in an oven at 60 ℃ to obtain a diaphragm, namely a sample S8.
Example 9
The embodiment provides a water-based nano composite modified material for a lithium battery diaphragm, and a preparation method of the water-based nano composite modified material comprises the following steps:
dispersing 160g of nano-cellulose with the diameter of 50nm (d 50-50 nm) and the length of 2 microns in 4kg of deionized water, and stirring and dispersing for later use; dispersing 800g of egg shell and shell composite powder (mass ratio is 2:1) with the diameter of 30-50nm into 5kg of deionized water, adding 0.1 wt% of polyvinyl alcohol (alcoholysis degree: 99 mol%, viscosity: 28mPa.s), stirring and dispersing for later use; and (3) stirring the nano cellulose pulp and the eggshell pulp at a high speed, homogenizing for 5 hours, adding 40g of 250nm alumina particles, and continuously stirring for 5 hours to obtain the nano cellulose/eggshell slurry.
The present invention also provides a light weight lithium battery separator, which is composed of a polyethylene porous membrane as a substrate and a modification layer attached to both sides of the polyethylene porous membrane, and the preparation method thereof is as follows:
preparing a polyethylene porous membrane with the thickness of 11 mu m, and roughening the polyethylene porous membrane by using a brush;
the prepared modified material is coated on two sides of the porous membrane at a coating rate of 50m/min, and then dried in an oven at 60 ℃ to obtain a diaphragm, namely a sample S9.
In the preparation of samples S1-S9, the heights of the doctor blades were kept consistent, and the post-treatment process was the same, so that the differences in the properties such as the thickness of the modified layer, the air permeability, etc., were derived from the differences in the modified material. The samples S1-S9 were characterized and the results are shown in Table 1.
Wherein the test method of the peeling strength refers to the national standard GB/T36363-2018;
the remaining performance indicators were determined according to methods conventional in the art.
TABLE 1 Performance characterization results for samples S1-S9
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (11)
1. The water-based nano composite modified material for the lithium battery diaphragm takes water as a liquid-phase component, and is characterized by further comprising a solid-phase component, wherein the solid-phase component comprises nano cellulose and a natural shell material;
the mass fraction of the nanocellulose and the natural shell material in the modified material is 0.1-15%, and the mass fraction of the nanocellulose in the solid phase component is 4-40%;
the mass percentage concentration c of the nanocellulose in the modified material and the length-diameter ratio L/d of the nanocellulose satisfy: c ═ 0.03 to 0.05 × L/d%, where L is the average length of the nanocellulose and d is the average diameter of the nanocellulose;
the natural shell material has a particle size d' which satisfies the average diameter d of the nanocellulose
2. The aqueous nanocomposite modification material for lithium battery separators as claimed in claim 1, wherein the nanocellulose has an average diameter of 20 to 50 nm;
and/or the natural shell material is in a powder form.
3. The aqueous nanocomposite modified material for lithium battery separators as claimed in claim 2, wherein the natural shell material is eggshell powder and/or shell powder.
4. The aqueous nanocomposite modified material for lithium battery separators according to any one of claims 1 to 3, wherein the solid phase component further comprises inorganic particles having a particle size of 180 to 300nm, and the inorganic particles account for 1 to 5 wt% of the natural shell material.
5. The aqueous nanocomposite modification material for lithium battery separators as claimed in claim 4, wherein the inorganic particles are one or more of alumina, titania and zirconia.
6. A preparation method of the aqueous nanocomposite modified material for the lithium battery separator as claimed in any one of claims 1 to 5, characterized by comprising a step of mixing a first slurry and a second slurry, wherein the first slurry comprises nanocellulose and water, and the second slurry comprises a natural shell material and water.
7. The method for preparing the aqueous nanocomposite modified material for lithium battery separators as claimed in claim 6, wherein the second slurry further comprises 0.01 to 0.2 wt% of a binder.
8. The preparation method of the aqueous nanocomposite modified material for the lithium battery separator according to claim 7, wherein the binder is polyvinyl alcohol having an alcoholysis degree of 97 to 99 mol% and a viscosity of 25 to 30 mPa.s.
9. A light weight lithium battery separator comprising a substrate, wherein the substrate is a porous film material, and at least one surface of the substrate is provided with a modification layer formed of the aqueous nanocomposite modification material for a lithium battery separator according to any one of claims 1 to 5.
10. The light weight lithium battery separator according to claim 9, wherein the thickness of the base material is 6 to 20 μm, and/or the thickness of the modification layer is 200 to 1000 nm.
11. A lithium ion battery, characterized in that the light weight lithium battery separator according to claim 9 or 10 is used as a separator.
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| PCT/CN2021/142368 WO2022161089A1 (en) | 2021-01-28 | 2021-12-29 | Aqueous nano-composite modification material for lithium battery separator and preparation method therefor, and lightweight lithium battery separator |
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| CN113013551B (en) * | 2021-01-28 | 2021-11-23 | 清华大学 | Water-based nano composite modified material for lithium battery diaphragm, preparation method of water-based nano composite modified material and light-weight lithium battery diaphragm |
| CN114171843B (en) * | 2021-11-18 | 2022-10-25 | 清华大学 | Water-based nano composite coating liquid for lithium ion battery diaphragm and lithium ion battery diaphragm |
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| CN113013551A (en) | 2021-06-22 |
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