阅读说明：本技术 一种安全锂离子电池隔膜、制备方法及锂离子电池 (Safe lithium ion battery diaphragm, preparation method and lithium ion battery ) 是由 刘文卿 臧世伟 于 2020-12-11 设计创作，主要内容包括：本发明公开了一种安全锂离子电池隔膜、制备方法及锂离子电池,涉及锂离子电池技术领域；该制备方法包括以下的步骤：S1、水性浆料的制备,将陶瓷材料、氧化镁、导电炭黑以及水性胶混合后搅拌均匀,得到水性浆料；S2、第一薄膜的制备,将反式-1,4-聚异戊二烯、顺丁橡胶、导电炭黑以及水溶性盐投入混炼造粒机中,进行混炼,制成记忆材料；将高分子聚合物颗粒与固体材料混合后放入吹膜机中,采用薄膜吹制法将高分子聚合物颗粒和固体材料的混合材料吹制成薄膜,将得到的薄膜过水并烘干后,得到第一薄膜；S3、第二薄膜的制备；S4、锂离子电池隔膜的制备；本发明的有益效果是：能够在温度升高时阻断电解液的反应,达到保护电池的作用。(The invention discloses a safe lithium ion battery diaphragm, a preparation method and a lithium ion battery, relating to the technical field of lithium ion batteries; the preparation method comprises the following steps: s1, preparing water-based slurry, namely mixing the ceramic material, the magnesium oxide, the conductive carbon black and the water-based adhesive, and then uniformly stirring to obtain the water-based slurry; s2, preparing a first film, namely putting trans-1, 4-polyisoprene, butadiene rubber, conductive carbon black and water-soluble salt into a mixing granulator, and mixing to prepare a memory material; mixing high molecular polymer particles and a solid material, putting the mixture into a film blowing machine, blowing the mixture of the high molecular polymer particles and the solid material into a film by adopting a film blowing method, and rinsing and drying the obtained film to obtain a first film; s3, preparing a second film; s4, preparing a lithium ion battery diaphragm; the invention has the beneficial effects that: the reaction of the electrolyte can be blocked when the temperature rises, and the effect of protecting the battery is achieved.)

1. A preparation method of a safe lithium ion battery diaphragm is characterized by comprising the following steps:

s1, preparing water-based slurry, namely mixing the ceramic material, the magnesium oxide, the conductive carbon black and the water-based adhesive, and then uniformly stirring to obtain the water-based slurry;

s2, preparing a first film, namely putting 50-60 parts of trans-1, 4-polyisoprene, 20-30 parts of butadiene rubber, 5-10 parts of conductive carbon black and 5-10 parts of water-soluble salt into a mixing granulator, and mixing to prepare a memory material with the particle size of 10-20 nm;

adding a memory material into a mixed solution of aluminum nitride and ethanol, stirring, filtering, drying the mixture, and calcining the dried substance under the protection of inert gas to obtain a solid material coated by the aluminum nitride;

mixing high molecular polymer particles and a solid material, putting the mixture into a film blowing machine, blowing the mixture of the high molecular polymer particles and the solid material into a film by adopting a film blowing method, and rinsing and drying the obtained film to obtain a first film;

s3, preparing a second film, namely, melting a halogen-containing compound mixed water-soluble salt, performing blow molding to form a film, and drying the film by water to obtain the second film;

s4, preparing a lithium ion battery diaphragm, namely coating the water-based slurry on the first film to form a water-based slurry layer on the surface of the first film so as to form a first composite film; coating the aqueous slurry on a second film to form an aqueous slurry layer on the surface of the second film, thereby forming a second composite film;

and drying the first composite film and the second composite film, and then compounding the water-based slurry layer on the first composite film and the water-based slurry layer on the second composite film together to obtain the lithium ion battery diaphragm.

2. The method according to claim 1, wherein in step S1, the ceramic material is β -spodumene powder, wherein the β -spodumene powder is 30-40 parts, the magnesium oxide is 20-35 parts, the conductive carbon black is 5-10 parts, and the aqueous gel is 25-45 parts.

3. The preparation method of the safe lithium ion battery separator according to claim 2, wherein the aqueous adhesive is a polyvinyl alcohol aqueous adhesive or aqueous polyurethane; the viscosity of the aqueous slurry ranges from 500-1000cps/25 ℃.

4. The method for preparing a lithium ion battery separator as claimed in claim 1, wherein in step S2, the temperature during mixing is 100-130 ℃, and the mixing time is 30-60 min; the drying temperature of the mixture is 80-100 ℃, and the calcining temperature is 300-400 ℃; the phase transition temperature of the memory material is 50-80 ℃.

5. The method of claim 1, wherein in steps S2 and S3, the film is dried at 50-60 ℃ for 10-20min after being washed with water.

6. The method according to claim 1, wherein in step S2, the polymer particles are PP or PET.

7. The method of claim 1, wherein in step S2, the aluminum nitride and the ethanol are mixed to form a turbid liquid, and the weight ratio of the aluminum nitride to the ethanol to the memory material is 3: 6: 1.

8. the method of claim 1, wherein in step S4, the first composite film and the second composite film are dried at a temperature of 50-100 ℃ for a time of 1-2 h.

9. The method as claimed in claim 1, wherein in step S4, the thickness of the aqueous slurry layer of the first composite film and the thickness of the aqueous slurry layer of the second composite film are both 250-500 nm.

10. A safe lithium ion battery diaphragm is characterized by comprising a first film, a second film and a water-based slurry layer, wherein the first film is attached to the second film through the water-based slurry layer;

the first film is embedded with a plurality of solid materials, the outside of the solid materials is an aluminum nitride shell, the inside of the aluminum nitride shell is a memory material, holes are formed in the memory material, and the first film is provided with first through holes communicated with the holes in the memory material; the second film is provided with a second through hole which penetrates through the second film.

11. The safe lithium ion battery separator according to claim 10, wherein the memory material is prepared by putting 50-60 parts of trans-1, 4-polyisoprene, 20-30 parts of butadiene rubber, 5-10 parts of conductive carbon black and 5-10 parts of water-soluble salt into a mixing granulator and mixing, and the particle size of the memory material is 10-20 nm.

12. The safe lithium ion battery separator according to claim 11, wherein the solid material is prepared by adding the memory material into a mixed solution of aluminum nitride and ethanol, stirring, filtering, drying the mixture, and calcining the dried material under the protection of inert gas.

13. The separator of claim 10, wherein the aqueous slurry layer is prepared by stirring 30-40 parts of β -spodumene powder, 20-35 parts of magnesium oxide, 5-10 parts of conductive carbon black and 25-45 parts of aqueous gel.

14. A lithium ion battery, characterized in that the separator of the lithium ion battery is obtained by the method for preparing a safe lithium ion battery separator according to any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of lithium ion batteries, in particular to a safe lithium ion battery diaphragm, a preparation method and a lithium ion battery.

Background

The lithium ion battery is widely applied to various electronic products due to large specific energy and long cycle life, but the defects of the lithium ion battery are gradually revealed along with the increase of the using amount of the lithium ion battery, and in recent years, the occurrence of battery ignition is often reported, thereby causing great damage to lives and properties of people.

Therefore, lithium ion batteries generally have two reasons for generating high heat and even explosion in the use process, one of which is that lithium dendrites generated on positive and negative electrodes pierce a diaphragm to cause internal short circuit, and the other one is mainly that when the batteries are improperly used, reactions generated in the batteries cannot be blocked in time, so that continuous reactions are caused, and dangerous results are caused.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides a safe lithium ion battery diaphragm, a preparation method and a lithium ion battery, which can prevent the reaction of electrolyte when the temperature rises so as to achieve the effect of protecting the battery.

The technical scheme adopted by the invention for solving the technical problems is as follows: the improvement of a preparation method of a safe lithium ion battery diaphragm is that the preparation method comprises the following steps:

s1, preparing water-based slurry, namely mixing the ceramic material, the magnesium oxide, the conductive carbon black and the water-based adhesive, and then uniformly stirring to obtain the water-based slurry;

s2, preparing a first film, namely putting 50-60 parts of trans-1, 4-polyisoprene, 20-30 parts of butadiene rubber, 5-10 parts of conductive carbon black and 5-10 parts of water-soluble salt into a mixing granulator, and mixing to prepare a memory material with the particle size of 10-20 nm;

adding a memory material into a mixed solution of aluminum nitride and ethanol, stirring, filtering, drying the mixture, and calcining the dried substance under the protection of inert gas to obtain a solid material coated by the aluminum nitride;

mixing high molecular polymer particles and a solid material, putting the mixture into a film blowing machine, blowing the mixture of the high molecular polymer particles and the solid material into a film by adopting a film blowing method, and rinsing and drying the obtained film to obtain a first film;

s3, preparing a second film, namely, melting a halogen-containing compound mixed water-soluble salt, performing blow molding to form a film, and drying the film by water to obtain the second film;

s4, preparing a lithium ion battery diaphragm, namely coating the water-based slurry on the first film to form a water-based slurry layer on the surface of the first film so as to form a first composite film; coating the aqueous slurry on a second film to form an aqueous slurry layer on the surface of the second film, thereby forming a second composite film;

and drying the first composite film and the second composite film, and then compounding the water-based slurry layer on the first composite film and the water-based slurry layer on the second composite film together to obtain the lithium ion battery diaphragm.

Further, in step S1, the ceramic material is β -spodumene powder, wherein the β -spodumene powder is 30-40 parts, the magnesium oxide is 20-35 parts, the conductive carbon black is 5-10 parts, and the aqueous gel is 25-45 parts.

Further, the aqueous adhesive is polyvinyl alcohol aqueous adhesive or aqueous polyurethane; the viscosity of the aqueous slurry ranges from 500-1000cps/25 ℃.

Further, in step S2, the temperature during mixing is 100-130 ℃, and the mixing time is 30-60 min; the drying temperature of the mixture is 80-100 ℃, and the calcining temperature is 300-400 ℃; the phase transition temperature of the memory material is 50-80 ℃.

Further, in step S2 and step S3, the film is dried for 10-20min at 50-60 ℃ after being washed with water.

Further, in step S2, the polymer particles are PP or PET.

Further, in step S2, the aluminum nitride and the ethanol are mixed to form a turbid liquid, and the weight ratio of the aluminum nitride to the ethanol to the memory material is 3: 6: 1

Further, in step S4, the drying temperature of the first composite film and the second composite film is 50-100 ℃, and the drying time is 1-2 hours.

Further, in step S4, the thicknesses of the aqueous slurry layer of the first composite film and the aqueous slurry layer of the second composite film are both 250-500 nm.

On the other hand, the invention also provides a safe lithium ion battery diaphragm, which is improved in that the safe lithium ion battery diaphragm comprises a first film, a second film and an aqueous slurry layer, wherein the first film is attached to the second film through the aqueous slurry layer;

the first film is embedded with a plurality of solid materials, the outside of the solid materials is an aluminum nitride shell, the inside of the aluminum nitride shell is a memory material, holes are formed in the memory material, and the first film is provided with first through holes communicated with the holes in the memory material; the second film is provided with a second through hole which penetrates through the second film.

In the structure, the memory material is prepared by putting 50-60 parts of trans-1, 4-polyisoprene, 20-30 parts of butadiene rubber, 5-10 parts of conductive carbon black and 5-10 parts of water-soluble salt into a mixing granulator and mixing, and the particle size of the memory material is 10-20 nm.

In the structure, the solid material is prepared by adding the memory material into a mixed solution of aluminum nitride and ethanol, stirring, filtering, drying the mixture, and calcining the dried substance under the protection of inert gas.

In the structure, the water-based slurry layer is prepared by stirring 30-40 parts of beta-spodumene powder, 20-35 parts of magnesium oxide, 5-10 parts of conductive carbon black and 25-45 parts of water-based adhesive.

On the other hand, the invention also provides a lithium ion battery, and the improvement is that the diaphragm of the lithium ion battery is obtained by the preparation method of the safety lithium ion battery diaphragm.

The invention has the beneficial effects that: the first film is filled with spherical particles (i.e. solid material), the first film is provided with first through holes communicated with the spherical particles, and the memory material in the solid material is provided with holes. When the temperature rises, the holes on the memory material can be automatically closed to prevent the electrolyte from further reacting, so that the battery is protected, and when the temperature drops, the channel is opened. When the temperature reaches a certain temperature, the diaphragm hole is automatically closed, so that the further reaction of the lithium ion electrolyte is prevented, and the use safety of the lithium ion battery is improved.

Drawings

Fig. 1 is a schematic flow chart of a method for preparing a safety lithium ion battery separator according to the present invention.

Fig. 2 is a schematic cross-sectional view of a first composite film of a safety lithium ion battery separator according to the present invention.

Fig. 3 is a schematic cross-sectional view of a second composite film of a safety lithium ion battery separator according to the present invention.

Fig. 4 is a schematic cross-sectional view of a safety lithium ion battery separator according to the present invention.

Fig. 5 is a schematic structural diagram of a solid material of a safety lithium ion battery separator according to the present invention.

Detailed Description

The invention is further illustrated with reference to the following figures and examples.

The conception, the specific structure, and the technical effects produced by the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, the features, and the effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. In addition, all the connection/connection relations referred to in the patent do not mean that the components are directly connected, but mean that a better connection structure can be formed by adding or reducing connection auxiliary components according to specific implementation conditions. All technical characteristics in the invention can be interactively combined on the premise of not conflicting with each other.

Example 1

Referring to fig. 1, the invention discloses a preparation method of a safety lithium ion battery separator, specifically, the method comprises the following steps:

s1, preparing water-based slurry, namely mixing the ceramic material, the magnesium oxide, the conductive carbon black and the water-based adhesive, and then uniformly stirring to obtain the water-based slurry;

in the embodiment, the ceramic material is beta-spodumene powder, wherein the beta-spodumene powder is 30 parts, the magnesium oxide is 20 parts, the conductive carbon black is 5 parts, and the aqueous gel is 25 parts; the aqueous adhesive is polyvinyl alcohol aqueous adhesive, water is used as solvent, and the viscosity range of the obtained aqueous slurry is 500-1000cps/25 ℃;

s2, preparing a first film, namely putting 50 parts of trans-1, 4-polyisoprene, 20 parts of butadiene rubber, 5 parts of conductive carbon black and 5 parts of water-soluble salt into a mixing granulator, mixing, wherein the mixing temperature is 100 ℃, the mixing time is 60min, and the memory material with the particle size of 10-20nm is prepared, the phase transition temperature of the memory material is 60 ℃, and the phase transition temperature of the memory material prepared by the process is 50-80 ℃ under the general condition; then, adding the memory material into a mixed solution of aluminum nitride and ethanol, stirring, carrying out suction filtration, and drying the mixture at the drying temperature of 80 ℃; calcining the dried substance under the protection of inert gas at the calcining temperature of 300 ℃ to obtain a solid material coated by aluminum nitride; in this embodiment, the aluminum nitride and the ethanol are mixed to form a turbid liquid, and the weight ratio of the aluminum nitride to the ethanol to the memory material is 3: 6: 1.

finally, mixing the high molecular polymer particles and the solid material, putting the mixture into a film blowing machine, blowing the mixture of the high molecular polymer particles and the solid material into a film by adopting a film blowing method, and rinsing and drying the obtained film to obtain a first film; in the step, after the film is washed by water, the film is dried for 20min at the temperature of 50 ℃; and, the above-mentioned high molecular polymer particle is PP;

in step S2, when water is passed through, after the water-soluble salt in the memory material is dissolved in the water, holes are formed in the memory material, and since the phase transition temperature of the memory material is generally between 50 ℃ and 80 ℃, when the temperature rises to this range, the memory material will deform to some extent, thereby closing the holes in the memory material; when the temperature is reduced, the memory material returns to the original state, so that when the temperature of the battery is too high due to incorrect use or other reasons, the diaphragm can be automatically sealed by the memory material, the lithium ion exchange of the positive electrode and the negative electrode is blocked, the purpose of blocking reaction is achieved, when the temperature reaches a normal level, the shape memory material can be automatically recovered, and the lithium ion battery can be normally used.

S3, preparing a second film, namely, melting a halogen-containing compound mixed water-soluble salt, performing blow molding to form the film, drying the film by water to obtain the second film, drying the film for 20min at the temperature of 50 ℃ after the film is washed by water, and dissolving the water-soluble salt after the film is washed by water to form fine through holes in the second film;

s4, preparing a lithium ion battery diaphragm, namely coating the aqueous slurry on the first film 10, and forming an aqueous slurry layer 30 on the surface of the first film 10 to form a first composite film 40, wherein the structure of the first composite film is shown in FIG. 2; coating the aqueous slurry on the second film 20 to form an aqueous slurry layer 30 on the surface of the second film 20, thereby forming a second composite film 50, the structure of which is shown in fig. 3; the thicknesses of the aqueous slurry layer 30 of the first composite film 40 and the aqueous slurry layer 30 of the second composite film 50 are both 250 nm;

after the first composite film 40 and the second composite film 50 are dried, the aqueous slurry layer 30 on the first composite film 40 and the aqueous slurry layer 30 on the second composite film 50 are composited together to obtain the lithium ion battery separator, and the structure of the lithium ion battery separator is shown in fig. 4. In this step, the drying temperature of the first and second composite films 40 and 50 is 50 ℃, and the drying time is 2 hours.

As shown in fig. 4 and 5, the invention further provides a safety lithium ion battery separator, which comprises a first film 10, a second film 20 and an aqueous slurry layer 30, wherein the first film 10 is attached to the second film 20 through the aqueous slurry layer 30; as shown in fig. 5, a plurality of solid materials 101 are embedded in the first thin film 10, the outer portion of the solid material 101 is an aluminum nitride shell 102, the inner portion of the aluminum nitride shell 102 is a memory material 103, and a hole is formed on the memory material 103, the first thin film 10 has a first through hole communicated with the hole on the memory material 103; the second film 20 has a second through hole.

In the embodiment, the memory material 103 is prepared by putting 50 parts of trans-1, 4-polyisoprene, 20 parts of butadiene rubber, 5 parts of conductive carbon black and 5 parts of water-soluble salt into a mixing granulator and mixing, and the particle size of the memory material 103 is 10-20 nm. Further, the solid material 101 is prepared by adding the memory material 103 into a mixed solution of aluminum nitride and ethanol, stirring, filtering, drying the mixture, and calcining the dried substance under the protection of inert gas. In the above embodiment, the aqueous slurry layer 30 is prepared by stirring 30 parts of β -spodumene powder, 20 parts of magnesium oxide, 5 parts of conductive carbon black and 25 parts of aqueous gel. Through the arrangement of the aqueous slurry layer 30, the beta-spodumene powder is a ceramic material, so that the strength of the diaphragm is increased, and the short circuit danger caused by the fact that the lithium dendrites generated on the positive electrode and the negative electrode pierce the diaphragm is avoided.

Based on this, in the safety lithium ion battery separator of the present invention, the first film 10 is filled with the spherical particles (i.e. the solid material 101), the first film 10 has first through holes communicating with the spherical particles, and the memory material 103 in the solid material 101 has holes. When the temperature rises, the holes on the memory material 103 can be automatically closed to prevent the electrolyte from further reacting, thereby achieving the effect of protecting the battery, and when the temperature drops, the channel is opened. When the temperature reaches a certain temperature, the holes of the diaphragm are automatically closed, so that the further reaction of the lithium ion electrolyte is prevented, and the lithium dendrite on the positive and negative pole pieces is prevented from puncturing the diaphragm to cause short circuit.

In addition, the invention also provides a lithium ion battery, and the diaphragm of the lithium ion battery is obtained by the preparation method of the safe lithium ion battery diaphragm.

Example 2

Referring to fig. 1, the invention discloses a preparation method of a safety lithium ion battery separator, specifically, the method comprises the following steps:

s1, preparing water-based slurry, namely mixing the ceramic material, the magnesium oxide, the conductive carbon black and the water-based adhesive, and then uniformly stirring to obtain the water-based slurry;

in the embodiment, the ceramic material is beta-spodumene powder, wherein the beta-spodumene powder is 40 parts, the magnesium oxide is 35 parts, the conductive carbon black is 10 parts, and the water-based adhesive is 45 parts; the aqueous adhesive is aqueous polyurethane, water is used as a solvent, and the viscosity range of the obtained aqueous slurry is 500-1000cps/25 ℃;

s2, preparing a first film, namely putting 60 parts of trans-1, 4-polyisoprene, 30 parts of butadiene rubber, 10 parts of conductive carbon black and 10 parts of water-soluble salt into a mixing granulator, mixing, wherein the mixing temperature is 130 ℃, the mixing time is 30min, and the memory material with the particle size of 10-20nm is prepared, the phase transition temperature of the memory material is 51 ℃, and the phase transition temperature of the memory material prepared by the process is 50-80 ℃ under the general condition; then, adding the memory material into a mixed solution of aluminum nitride and ethanol, stirring, carrying out suction filtration, and drying the mixture at the drying temperature of 100 ℃; calcining the dried substance under the protection of inert gas at 400 ℃ to obtain a solid material coated by aluminum nitride; in this embodiment, the aluminum nitride and the ethanol are mixed to form a turbid liquid, and the weight ratio of the aluminum nitride to the ethanol to the memory material is 3: 6: 1.

finally, mixing the high molecular polymer particles and the solid material, putting the mixture into a film blowing machine, blowing the mixture of the high molecular polymer particles and the solid material into a film by adopting a film blowing method, and rinsing and drying the obtained film to obtain a first film; in the step, after the film is washed by water, the film is dried for 10min at the temperature of 60 ℃; and, the above-mentioned high molecular polymer granule is PET;

in step S2, when water is passed through, after the water-soluble salt in the memory material is dissolved in the water, holes are formed in the memory material, and since the phase transition temperature of the memory material is generally between 50 ℃ and 80 ℃, when the temperature rises to this range, the memory material will deform to some extent, thereby closing the holes in the memory material; when the temperature is reduced, the memory material returns to the original state, so that when the temperature of the battery is too high due to incorrect use or other reasons, the diaphragm can be automatically sealed by the memory material, the lithium ion exchange of the positive electrode and the negative electrode is blocked, the purpose of blocking reaction is achieved, when the temperature reaches a normal level, the shape memory material can be automatically recovered, and the lithium ion battery can be normally used.

S3, preparing a second film, namely, melting a halogen-containing compound mixed water-soluble salt, performing blow molding to form the film, rinsing and drying to obtain the second film, wherein in the step, the film is rinsed and dried at the temperature of 60 ℃ for 10 min;

s4, preparing a lithium ion battery diaphragm, namely coating the aqueous slurry on the first film 10, and forming an aqueous slurry layer 30 on the surface of the first film 10 to form a first composite film 40, wherein the structure of the first composite film is shown in FIG. 2; coating the aqueous slurry on the second film 20 to form an aqueous slurry layer 30 on the surface of the second film 20, thereby forming a second composite film 50, the structure of which is shown in fig. 3; the thickness of the aqueous slurry layer 30 of the first composite film 40 and the thickness of the aqueous slurry layer 30 of the second composite film 50 are both 500 nm;

after the first composite film 40 and the second composite film 50 are dried, the aqueous slurry layer 30 on the first composite film 40 and the aqueous slurry layer 30 on the second composite film 50 are composited together to obtain the lithium ion battery separator, and the structure of the lithium ion battery separator is shown in fig. 4. In this step, the drying temperature of the first and second composite films 40 and 50 is 100 ℃, and the drying time is 1 h.

As shown in fig. 4 and 5, the invention further provides a safety lithium ion battery separator, which comprises a first film 10, a second film 20 and an aqueous slurry layer 30, wherein the first film 10 is attached to the second film 20 through the aqueous slurry layer 30; as shown in fig. 5, a plurality of solid materials 101 are embedded in the first thin film 10, the outer portion of the solid material 101 is an aluminum nitride shell 102, the inner portion of the aluminum nitride shell 102 is a memory material 103, and a hole is formed on the memory material 103, the first thin film 10 has a first through hole communicated with the hole on the memory material 103; the second film 20 has a second through hole.

In the embodiment, the memory material 103 is prepared by putting 60 parts of trans-1, 4-polyisoprene, 30 parts of butadiene rubber, 10 parts of conductive carbon black and 10 parts of water-soluble salt into a mixing granulator and mixing, and the particle size of the memory material 103 is 10-20 nm. Further, the solid material 101 is prepared by adding the memory material 103 into a mixed solution of aluminum nitride and ethanol, stirring, filtering, drying the mixture, and calcining the dried substance under the protection of inert gas. In the above embodiment, the aqueous slurry layer 30 is prepared by stirring 40 parts of β -spodumene powder, 35 parts of magnesium oxide, 10 parts of conductive carbon black and 45 parts of aqueous gel. Through the arrangement of the aqueous slurry layer 30, the beta-spodumene powder is a ceramic material, so that the strength of the diaphragm is increased, and the short circuit danger caused by the fact that the lithium dendrites generated on the positive electrode and the negative electrode pierce the diaphragm is avoided.

Based on this, in the safety lithium ion battery separator of the present invention, the first film 10 is filled with the spherical particles (i.e. the solid material 101), the first film 10 has first through holes communicating with the spherical particles, and the memory material 103 in the solid material 101 has holes. When the temperature rises, the holes on the memory material 103 can be automatically closed to prevent the electrolyte from further reacting, thereby achieving the effect of protecting the battery, and when the temperature drops, the channel is opened. When the temperature reaches a certain temperature, the holes of the diaphragm are automatically closed, so that the further reaction of the lithium ion electrolyte is prevented, and the lithium dendrite on the positive and negative pole pieces is prevented from puncturing the diaphragm to cause short circuit.

In addition, the invention also provides a lithium ion battery, and the diaphragm of the lithium ion battery is obtained by the preparation method of the safe lithium ion battery diaphragm.

Example 3

Referring to fig. 1, the invention discloses a preparation method of a safety lithium ion battery separator, specifically, the method comprises the following steps:

s1, preparing water-based slurry, namely mixing the ceramic material, the magnesium oxide, the conductive carbon black and the water-based adhesive, and then uniformly stirring to obtain the water-based slurry;

in the embodiment, the ceramic material is beta-spodumene powder, wherein the beta-spodumene powder is 35 parts, the magnesium oxide is 30 parts, the conductive carbon black is 7 parts, and the water-based adhesive is 35 parts; the aqueous adhesive is polyvinyl alcohol aqueous adhesive, water is used as solvent, and the viscosity range of the obtained aqueous slurry is 500-1000cps/25 ℃;

s2, preparing a first film, namely putting 55 parts of trans-1, 4-polyisoprene, 25 parts of butadiene rubber, 7 parts of conductive carbon black and 7 parts of water-soluble salt into a mixing granulator, mixing, wherein the mixing temperature is 120 ℃, the mixing time is 45min, and the memory material with the particle size of 10-20nm is prepared, the phase transition temperature of the memory material is 70 ℃, and the phase transition temperature of the memory material prepared by the process is 50-80 ℃ under the general condition; then, adding the memory material into a mixed solution of aluminum nitride and ethanol, stirring, carrying out suction filtration, and drying the mixture at the drying temperature of 90 ℃; calcining the dried substance under the protection of inert gas at 350 ℃ to obtain a solid material coated by aluminum nitride; in this embodiment, the aluminum nitride and the ethanol are mixed to form a turbid liquid, and the weight ratio of the aluminum nitride to the ethanol to the memory material is 3: 6: 1.

finally, mixing the high molecular polymer particles and the solid material, putting the mixture into a film blowing machine, blowing the mixture of the high molecular polymer particles and the solid material into a film by adopting a film blowing method, and rinsing and drying the obtained film to obtain a first film; in the step, after the film is washed by water, the film is dried for 30min at the temperature of 55 ℃; and, the above-mentioned high molecular polymer particle is PP;

in step S2, when water is passed through, after the water-soluble salt in the memory material is dissolved in the water, holes are formed in the memory material, and since the phase transition temperature of the memory material is generally between 50 ℃ and 80 ℃, when the temperature rises to this range, the memory material will deform to some extent, thereby closing the holes in the memory material; when the temperature is reduced, the memory material returns to the original state, so that when the temperature of the battery is too high due to incorrect use or other reasons, the diaphragm can be automatically sealed by the memory material, the lithium ion exchange of the positive electrode and the negative electrode is blocked, the purpose of blocking reaction is achieved, when the temperature reaches a normal level, the shape memory material can be automatically recovered, and the lithium ion battery can be normally used.

S3, preparing a second film, namely, melting a halogen-containing compound mixed water-soluble salt, performing blow molding to form the film, drying the film by water to obtain the second film, and drying the film for 15min at the temperature of 55 ℃ after the film is dried by water in the step;

s4, preparing a lithium ion battery diaphragm, namely coating the aqueous slurry on the first film 10, and forming an aqueous slurry layer 30 on the surface of the first film 10 to form a first composite film 40, wherein the structure of the first composite film is shown in FIG. 2; coating the aqueous slurry on the second film 20 to form an aqueous slurry layer 30 on the surface of the second film 20, thereby forming a second composite film 50, the structure of which is shown in fig. 3; the thickness of the aqueous slurry layer 30 of the first composite film 40 and the thickness of the aqueous slurry layer 30 of the second composite film 50 are both 375 nm;

after the first composite film 40 and the second composite film 50 are dried, the aqueous slurry layer 30 on the first composite film 40 and the aqueous slurry layer 30 on the second composite film 50 are composited together to obtain the lithium ion battery separator, and the structure of the lithium ion battery separator is shown in fig. 4. In this step, the drying temperature of the first and second composite films 40 and 50 is 75 ℃, and the drying time is 1.5 h.

As shown in fig. 4 and 5, the invention further provides a safety lithium ion battery separator, which comprises a first film 10, a second film 20 and an aqueous slurry layer 30, wherein the first film 10 is attached to the second film 20 through the aqueous slurry layer 30; as shown in fig. 5, a plurality of solid materials 101 are embedded in the first thin film 10, the outer portion of the solid material 101 is an aluminum nitride shell 102, the inner portion of the aluminum nitride shell 102 is a memory material 103, and a hole is formed on the memory material 103, the first thin film 10 has a first through hole communicated with the hole on the memory material 103; the second film 20 has a second through hole.

In the embodiment, the memory material 103 is prepared by putting 55 parts of trans-1, 4-polyisoprene, 25 parts of butadiene rubber, 7 parts of conductive carbon black and 7 parts of water-soluble salt into a mixing granulator and mixing, and the particle size of the memory material 103 is 10-20 nm. Further, the solid material 101 is prepared by adding the memory material 103 into a mixed solution of aluminum nitride and ethanol, stirring, filtering, drying the mixture, and calcining the dried substance under the protection of inert gas. In the above embodiment, the aqueous slurry layer 30 is prepared by stirring 35 parts of β -spodumene powder, 30 parts of magnesium oxide, 7 parts of conductive carbon black and 35 parts of aqueous gel. Through the arranged aqueous slurry layer 30, the beta-spodumene powder is a ceramic material, so that the strength of the diaphragm is increased, the short circuit danger caused by the fact that the lithium dendrites generated on the positive electrode and the negative electrode pierce the diaphragm is avoided, and the lithium ions can not be influenced to freely pass through the thinner aqueous slurry layer.

Based on this, in the safety lithium ion battery separator of the present invention, the first film 10 is filled with the spherical particles (i.e. the solid material 101), the first film 10 has first through holes communicating with the spherical particles, and the memory material 103 in the solid material 101 has holes. When the temperature rises, the holes on the memory material 103 can be automatically closed to prevent the electrolyte from further reacting, thereby achieving the effect of protecting the battery, and when the temperature drops, the channel is opened. When the temperature reaches a certain temperature, the holes of the diaphragm are automatically closed, so that the further reaction of the lithium ion electrolyte is prevented, and the lithium dendrite on the positive and negative pole pieces is prevented from puncturing the diaphragm to cause short circuit.

In addition, the invention also provides a lithium ion battery, and the diaphragm of the lithium ion battery is obtained by the preparation method of the safe lithium ion battery diaphragm.

Example 4

Referring to fig. 1, the invention discloses a preparation method of a safety lithium ion battery separator, specifically, the method comprises the following steps:

s1, preparing water-based slurry, namely mixing the ceramic material, the magnesium oxide, the conductive carbon black and the water-based adhesive, and then uniformly stirring to obtain the water-based slurry;

in the embodiment, the ceramic material is beta-spodumene powder, wherein 32 parts of beta-spodumene powder, 35 parts of magnesium oxide, 10 parts of conductive carbon black and 30 parts of water-based adhesive are used; the aqueous adhesive is aqueous polyurethane, water is used as a solvent, and the viscosity range of the obtained aqueous slurry is 500-1000cps/25 ℃;

s2, preparing a first film, namely putting 58 parts of trans-1, 4-polyisoprene, 28 parts of butadiene rubber, 10 parts of conductive carbon black and 10 parts of water-soluble salt into a mixing granulator, mixing, wherein the mixing temperature is 130 ℃, the mixing time is 30min, and the memory material with the particle size of 10-20nm is prepared, the phase transition temperature of the memory material is 53 ℃, and the phase transition temperature of the memory material prepared by the process is 50-80 ℃ under the general condition; then, adding the memory material into a mixed solution of aluminum nitride and ethanol, stirring, carrying out suction filtration, and drying the mixture at the drying temperature of 100 ℃; calcining the dried substance under the protection of inert gas at 400 ℃ to obtain a solid material coated by aluminum nitride; in this embodiment, the aluminum nitride and the ethanol are mixed to form a turbid liquid, and the weight ratio of the aluminum nitride to the ethanol to the memory material is 3: 6: 1.

finally, mixing the high molecular polymer particles and the solid material, putting the mixture into a film blowing machine, blowing the mixture of the high molecular polymer particles and the solid material into a film by adopting a film blowing method, and rinsing and drying the obtained film to obtain a first film; in the step, after the film is washed by water, the film is dried for 10min at the temperature of 60 ℃; and, the above-mentioned high molecular polymer granule is PET;

in step S2, when water is passed through, after the water-soluble salt in the memory material is dissolved in the water, holes are formed in the memory material, and since the phase transition temperature of the memory material is generally between 50 ℃ and 80 ℃, when the temperature rises to this range, the memory material will deform to some extent, thereby closing the holes in the memory material; when the temperature is reduced, the memory material returns to the original state, so that when the temperature of the battery is too high due to incorrect use or other reasons, the diaphragm can be automatically sealed by the memory material, the lithium ion exchange of the positive electrode and the negative electrode is blocked, the purpose of blocking reaction is achieved, when the temperature reaches a normal level, the shape memory material can be automatically recovered, and the lithium ion battery can be normally used.

S3, preparing a second film, namely, melting a halogen-containing compound mixed water-soluble salt, performing blow molding to form the film, rinsing and drying to obtain the second film, wherein in the step, the film is rinsed and dried at the temperature of 60 ℃ for 10 min;

s4, preparing a lithium ion battery diaphragm, namely coating the aqueous slurry on the first film 10, and forming an aqueous slurry layer 30 on the surface of the first film 10 to form a first composite film 40, wherein the structure of the first composite film is shown in FIG. 2; coating the aqueous slurry on the second film 20 to form an aqueous slurry layer 30 on the surface of the second film 20, thereby forming a second composite film 50, the structure of which is shown in fig. 3; the thickness of the aqueous slurry layer 30 of the first composite film 40 and the thickness of the aqueous slurry layer 30 of the second composite film 50 are both 500 nm;

after the first composite film 40 and the second composite film 50 are dried, the aqueous slurry layer 30 on the first composite film 40 and the aqueous slurry layer 30 on the second composite film 50 are composited together to obtain the lithium ion battery separator, and the structure of the lithium ion battery separator is shown in fig. 4. In this step, the drying temperature of the first and second composite films 40 and 50 is 100 ℃, and the drying time is 1 h.

As shown in fig. 4 and 5, the invention further provides a safety lithium ion battery separator, which comprises a first film 10, a second film 20 and an aqueous slurry layer 30, wherein the first film 10 is attached to the second film 20 through the aqueous slurry layer 30; as shown in fig. 5, a plurality of solid materials 101 are embedded in the first thin film 10, the outer portion of the solid material 101 is an aluminum nitride shell 102, the inner portion of the aluminum nitride shell 102 is a memory material 103, and a hole is formed on the memory material 103, the first thin film 10 has a first through hole communicated with the hole on the memory material 103; the second film 20 has a second through hole.

In the embodiment, the memory material 103 is prepared by putting 58 parts of trans-1, 4-polyisoprene, 28 parts of butadiene rubber, 10 parts of conductive carbon black and 10 parts of water-soluble salt into a mixing granulator and mixing, and the particle size of the memory material 103 is 10-20 nm. Further, the solid material 101 is prepared by adding the memory material 103 into a mixed solution of aluminum nitride and ethanol, stirring, filtering, drying the mixture, and calcining the dried substance under the protection of inert gas. In the above embodiment, the aqueous slurry layer 30 is prepared by stirring 32 parts of β -spodumene powder, 35 parts of magnesium oxide, 10 parts of conductive carbon black and 30 parts of aqueous paste. Through the arrangement of the aqueous slurry layer 30, the beta-spodumene powder is a ceramic material, so that the strength of the diaphragm is increased, and the short circuit danger caused by the fact that the lithium dendrites generated on the positive electrode and the negative electrode pierce the diaphragm is avoided.

Based on this, in the safety lithium ion battery separator of the present invention, the first film 10 is filled with the spherical particles (i.e. the solid material 101), the first film 10 has first through holes communicating with the spherical particles, and the memory material 103 in the solid material 101 has holes. When the temperature rises, the holes on the memory material 103 can be automatically closed to prevent the electrolyte from further reacting, thereby achieving the effect of protecting the battery, and when the temperature drops, the channel is opened. When the temperature reaches a certain temperature, the holes of the diaphragm are automatically closed, so that the further reaction of the lithium ion electrolyte is prevented, and the lithium dendrite on the positive and negative pole pieces is prevented from puncturing the diaphragm to cause short circuit.

In addition, the safety lithium ion battery separator prepared by the invention is compared with the separator purchased in the prior art by combining the above examples 1 to 4.

Separator of comparative example: the common diaphragm sold in the market is adopted, the porosity of the diaphragm is 85%, the pore diameter is 50%, and the material is a PP film.

Separator of the example: the lithium ion battery separators provided in examples 1-4 were used.

Preparation of lithium ion battery of comparative example separator: mixing graphite, PVDF and n-butyl acetate according to a ratio of 2:1:2 to prepare negative active slurry, coating the negative active slurry on a conductive film plated with metal copper, wherein the thickness of the conductive film is 3um, copper layers of 1um are plated on two surfaces of the conductive film to obtain a negative pole piece, preparing lithium iron phosphate, PVDF and ethyl acetate into a positive active material according to a ratio of 5:2:3, coating the positive active material on the film plated with metal aluminum, wherein the thickness of the film is also 3um, aluminum layers plated on two surfaces of the film are also 1um, a diaphragm adopts a polyethylene film with the porosity of 85% and the pore diameter of 50nm, an electrolyte is prepared from EC + DMC + EMC solution of 1.0M LiPF6, and all the assembly is carried out in a glove box.

Preparation of the lithium ion batteries of the examples: the preparation of the examples is identical to the preparation of the comparative examples except that the separator used is a separator provided by the present invention.

And (3) overshoot test: the cells obtained in the above examples and comparative examples were constant-current charged at 3C rate to 5V recording cell state. The experimental results are as follows:

sample (I)	3C-5C overcharge test
		Comparative example 1	Smoking
Comparative example 2	Smoking
		Comparative example 3	On fire
Comparative example 4	Smoking
		Example 1	Without ignitionAnd smoking, etc
Example 2	No fire and smoke
		Example 3	No fire and smoke
Example 4	No fire and smoke

In addition, the invention also provides a lithium ion battery, and the diaphragm of the lithium ion battery is obtained by the preparation method of the safe lithium ion battery diaphragm.

While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.