Patent Application
20240421431
The present invention relates to the technical field of battery separators, and in particular to a modified composite separator and a preparation method thereof.
Lithium-ion battery is a new type of green secondary battery that was successfully developed and commercialized in 1990. Compared with traditional lead-acid batteries, cadmium-nickel batteries and the like, lithium-ion batteries have the advantages of high energy density, high working voltage, long cycle life, small size, no memory effect, fast charging and discharging, and environmental protection. Lithium-ion batteries have been widely used in 3C products such as mobile phones, laptop computers and electrical tools, and have become the main developing direction of secondary batteries at current stage. In recent years, with the implementation of new energy strategies around the world, high-energy-density lithium-ion battery has been developed more rapidly, wherein its energy density has been increased to the level of 300 Wh/kg, and its applications have been extended rapidly from traditional small 3C electronic field to large power equipment field such as new energy electric vehicles, energy storage, large unmanned aerial vehicles, ships, pure electric aircrafts and the like. The rapid development of 3C products and large power equipment, especially new energy electric vehicles, also has put forward higher requirements for the specific capacity, safety and the like of lithium-ion batteries.
Lithium-ion batteries are mainly composed of positive/negative electrode materials, electrolyte and separator. The separator is an important part of a lithium-ion battery which separates the positive electrode from the negative electrode, prevents short-circuiting of the battery, and allows lithium ions to pass through freely. The separator plays an important role in improving the overall performance of the battery and is known as the “third electrode” of the battery in the battery industry. Although the separator does not participate in the battery reaction, its structure and performance have an important influence on the manufacturing, performance, service life, reliability and safety of the battery. Traditional lithium-ion battery separators generally use polyolefin materials represented by polyethylene and polypropylene, which are prepared through wet, dry uniaxil stretching, dry diaxil stretching and other processes and have good tensile properties, pore size distribution and the like. Currently, traditional polyolefin microporous separators are commonly used as separators for lithium-ion batteries due to their excellent chemical stability, thickness, and mechanical strength. However, these separators undergo severe thermal shrinkage at a higher temperature. This problem is fatal to the safety of battery because it may lead to the contacting of positive and negative electrodes inside battery and therefor short circuit, and eventually lead to fire or even explosion. Moreover, the polarity of the separator is completely different from that of the electrolyte. The separator is a non-polar material and the electrolyte is polar, making it difficult for the separator to be wetted by the electrolyte, resulting in poor wettability of the separator. The inadequate wettability and low porosity of the separator will significantly hinder the conductivity of lithium ions, consequently affecting the overall performance of lithium-ion batteries. These problems of polyolefin-based separators have become critical obstacles in the development of safe, high-power lithium-ion batteries.
Therefore, the development of a new separator material with high temperature resistance and good wettability has become a key issue that the lithium battery industry urgently needs to solve and one of the most important research directions, particularly for the development of large-capacity and high-energy-density lithium-ion batteries.
In view of above situation, the current modification methods mainly include blending modification, composite modification, coating modification, ion modification and other modification methods. Surface coating is one of the most important and commonly used methods. The surface of the polyolefin membrane is usually coated with ceramic coatings, such as aluminum oxide (Al2O3), silicon dioxide (SiO2), titanium dioxide (TiO2), etc. The coating can significantly improve the wettability of the separator by the electrolyte and temperature resistance of the separator. However, ceramic-coated modified polyolefin separators continue to face several challenges. For example, inorganic ceramics have poor compatibility with the substrate, and the ceramic coating is easy to peel off. In addition, the density of the ceramic layer adds weight, and the insulating property of ceramic is poor and accordingly the dielectric property is insufficient, especially when the base membrane thins or melts. Another problem is that the inorganic coating is a powdery agglomeration structure of particles, which itself cannot form a continuous self-supporting structure. Therefore, inorganic coating usually shows problems of easy powder loss and coating peeling during usage. More importantly, the inorganic particle layer of the inorganic coated separator at high temperature will generally pulverize and break, leading to separator breakdown. It cannot suppress the occurrence of thermal runaway and cannot meet the requirements of high heat resistance and high thermal dimensional stability of the separator in lithium-ion batteries.
Considering the aforementioned challenges, there are more and more studies on using high temperature resistant polymers as coating materials, and commonly used polymers include PVDF, PMMA, PEI, etc. For example, patent CN104993089 reports an aramid-coated lithium-ion battery separator and its preparation method. According to the patent, an aramid solution, an emulsifier solution, and a binder are mixed uniformly to obtain an aramid slurry, and then the resulting polymer colloidal fluid is coated onto the surface of the polyolefin separator. The thermal dimensional stability of the separator is improved to a certain extent and the safety and reliability of lithium-ion batteries are improved. However, the organic polymer in this method has an insufficient temperature resistance and the improvement of thermal dimensional stability is insufficient.
In view of the above shortcomings, it is necessary to innovate existing coatings and develop new coating technologies to solve the problem of pulverizing and breaking of the inorganic particle coating at high temperature, thereby improving the temperature resistance of the separator and preparing new separator materials with heat resistance and high thermal dimensional stability, so as to meet the urgent needs of high-energy-density lithium-ion batteries for high-temperature-resistant separators and high safety.
The present invention provides a modified composite separator, wherein the coated modified composite separator includes a base membrane and a coating, wherein the coating is coated on either one side or both sides of the base membrane, and the coating comprises at least two types of the three following components: high temperature resistant polymer microspheres, high temperature resistant polymer nanofibers and inorganic particles. Upon the incorporation of the high temperature resistant polymer into the coating, the separator shows good thermal protection effect and high temperature thermal dimensional stability because the polymer is an organic substance and is more intimately combined with the binder and the like, and at the same time, the high temperature resistant polymer has a lower density, and can increase the liquid retention rate of the separator and can improve the cycle performance and temperature resistance of the battery.
The base membrane is a polymer base membrane or a polymer base membrane coated with inorganic particles. The particle size of the high temperature resistant polymer microspheres is 3-20000 nm, preferably 5-18000 nm, more preferably 8-15000 nm; more preferably, the particle size of the high temperature resistant polymer microspheres is 3-5000 nm, preferably 5-3000 nm, more preferably 8-2000 nm. The diameter of the high temperature resistant polymer nanofibers is 5-1500 nm, preferably 6-1450 nm, and more preferably 8-1350 nm. The length of the high temperature resistant polymer nanofibers is 0.5-1000 μm, preferably 0.6-950 μm, and more preferably 1.0-900 μm. The thickness of the base membrane is 1.5-40 μm, preferably 2.0-35 μm, more preferably 3.5-30 μm. The thickness of the coating is 0.2-10 μm, preferably 0.3-9 μm, more preferably 0.5-8 μm. The total thickness of the modified composite separator is 2.0-45 μm, preferably 2.5-40 μm, and most preferably 3-36 μm.
The present invention also provides a method for preparing a coated modified composite separator, including the following steps:
In one aspect, the present invention also provides a coating slurry comprising a slurry solvent and at least two of the following: high temperature resistant polymer microspheres, high temperature resistant polymer nanofibers and inorganic particles. The coating slurry is used to prepare a coated modified composite separator through a coating method.
In one aspect, the present invention also provides a lithium-ion battery, characterized in that the lithium-ion battery includes a positive electrode, a negative electrode, an electrolyte and a coated modified composite separator.
The coated modified composite separator and its preparation method of the present invention have one, more or even all of the following beneficial effects:
The present invention provides a high temperature resistant polymer coated modified composite separator, wherein the coating of the modified composite separator is made of high temperature resistant polymer microspheres, high temperature resistant polymer microspheres and high temperature resistant polymer nanofibers, or high temperature resistant polymer microspheres or high temperature resistant polymer nanofibers and inorganic particles. The high temperature resistant polymer provides good thermal protection effect for the separator due to its good adhesion with binder and the like, and can significantly improve the temperature resistance property of the separator and safety property of the battery.
The density of high temperature resistant polymer is significantly lower than that of inorganic particles, which greatly reduces the weight of the coating and the weight per unit area of the separator and which is beneficial to increase the energy density of the battery.
The modified composite separator prepared in the present invention has higher electrolyte absorption rate and liquid retention rate because the high temperature resistant polymer and the electrolyte are both organic substances with polar structures, which can improve the rate capability and cycle life of the battery.
The coating technology provided by the present invention can be applied on any substrate separator to achieve coating formation, and has a wide range of applications. The forming process is simple and can be achieved through any one of electrostatic spraying, blade coating, extrusion coating, transfer coating, dip coating, wire rod coating, gravure or micro-gravure coating, which is easy to conduct in an industrial scale and has a great industrialization prospect.
The present invention prepares high temperature resistant polymer with fiber/microsphere composite morphology by using template method, spray drying technology, electrospinning technology, blowing spinning technology or blowing-assisted electrospinning. The preparation process is simple and efficient.
The incorporation of high temperature resistant polymer nanofibers can form a network structure, increase the integrity of the coating, and avoid the pulverizing problem of pure microsphere structure caused by binder failure at high temperature.
The high temperature-resistant polymer can enhance the thermal stability of polyolefin separators. Moreover, at high temperatures, polyolefins undergo thermal melting, effectively achieving thermal sealing/thermally pore closure, greatly enhancing the safety of the battery.
In the case where the coating of the modified composite separator is formed by mixing high temperature resistant polymer nanofibers and inorganic particles, a “rebar-concrete” structure is formed after the mixing of high temperature resistant polymer nanofibers and ceramics, and the nanofibers form a network such that the mixed coating as a whole has continuous self-supporting characteristic and thus the inorganic coating can maintain a good integrity without braking and pulverizing even the base membrane melts at high temperature, and showing an excellent thermal protection effect. It solves the problem of pulverizing and breaking of a pure inorganic particle coating at high temperature, which can significantly improve the temperature resistance of the separator and battery safety.
In the case where the modified composite separator has high temperature resistant polymer nanofibers, the high-temperature thermal dimensional stability is significantly improved, the overall strength of the mixed coating is significantly increased by the incorporation of high temperature resistant polymer nanofibers, and at the same time, the weight of the coating and the weight of the separator per unit area is reduced greatly since the density of the high temperature resistant polymer nanofibers is significantly lower than that of inorganic particles. The modified composite separator has the characteristic of light weight, facilitating the improvement of the energy density of the battery.
In the case where the modified composite separator has high temperature resistant polymer nanofibers, the separator has higher electrolyte absorption rate and electrolyte retention rate because the high temperature resistant polymer nanofibers forms a network structure in the mixed coating, which can improve the rate capability and cycle life of the battery.
Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
1. A coated modified composite separator, characterized in that,
2. The coated modified composite separator according to embodiment 1, characterized in that the high temperature resistant polymer includes polyimide.
3. The coated modified composite separator according to embodiment 1, characterized in that the particle size of the high temperature resistant polymer microspheres is 3-20000 nm, preferably 5-18000 nm, more preferably 8-15000 nm; more preferably, the particle size of the high temperature resistant polymer microspheres is 3-5000 nm, preferably 5-3000 nm, and more preferably 8-2000 nm.
4. The coated modified composite separator according to embodiment 1, characterized in that the thickness of the base membrane is 1.5-40 μm, preferably 2.0-35 μm, and more preferably 3.5-30 μm.
5. The coated modified composite separator according to embodiment 1, characterized in that the total thickness of the modified composite separator is 2.0-45 μm, preferably 2.5-40 μm, and most preferably 3-36 μm.
6. The coated modified composite separator according to embodiment 1, characterized in that the thickness of the coating is 0.2-10 μm, preferably 0.3-9 μm, and more preferably 0.5-8 μm.
7. The coated modified composite separator according to embodiment 1 or 2, characterized in that the base membrane is a polyolefin base membrane or a polyolefin base membrane coated with inorganic particles.
8. The coated modified composite separator according to embodiment 2, characterized in that the coating comprises polyimide nanofibers/polyimide microspheres.
9. The coated modified composite separator according to embodiment 7, characterized in that the thickness of the polyolefin base membrane coated with inorganic particles is 3-40 μm.
10. The coated modified composite separator according to embodiment 8, characterized in that the diameter of the polyimide nanofibers in the polyimide coating is 20-1000 nm.
11. The coated modified composite separator according to embodiment 1, characterized in that the coating comprises high temperature resistant polymer microspheres and inorganic particles, and the weight ratio of the high temperature resistant polymer microspheres to the inorganic particles is 0.1-100:99.9-0, preferably 0.1-99.9:99.9-0.1.
12. The coated modified composite separator according to embodiment 11, characterized in that the weight ratio of high temperature resistant polymer microspheres to inorganic particles in the coating is 1-100:99-0, preferably 5-100:95-0, most preferably 30-100:70-0, and even more preferably, the weight ratio of high temperature resistant polymer microspheres to inorganic particles in the coating is 1-99.9:99-0.1, preferably 5-99.9:95-0.1, most preferably 30-99.9:70-0.1.
13. The coated modified composite separator of embodiment 11, wherein the base membrane is at least one of a polymer base membrane and an base membrane coated with inorganic particles;
14. The coated modified composite separator according to embodiment 13, characterized in that the polymer base membrane includes a single-layer membrane, a double-layer membrane or a multi-layer membrane, and the polymer base membrane contained in each layer are the same or different.
15. The coated modified composite separator according to any one of embodiments 11-14, characterized in that the high temperature resistant polymer microspheres include at least one of the following: unmodified high temperature resistant polymer microspheres, surface modified high temperature resistant polymer microspheres, and inorganic hybrid high temperature resistant polymer microspheres.
16. The coated modified composite separator according to embodiment 15, characterized in that the polymers in the unmodified high temperature resistant polymer microspheres, surface modified high temperature resistant polymer microspheres, and inorganic hybrid high temperature resistant polymer microspheres include at least one of: P84, polyetherimide, polyphosphazene, polyacrylonitrile, polystyrene, polyvinylidene fluoride, polyvinylidene fluoride copolymer, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polytetrafluoroethylene, polyimide, polyester, cellulose, polyether ether ketone, polyaryl ether, polyamide, and polybenzimidazole.
17. The coated modified composite separator according to embodiment 16, characterized in that the surface modified high temperature resistant polymer microspheres include at least one of inorganic surface-modified high temperature resistant polymer microspheres, high temperature resistant polymer microspheres with polar groups after surface treating, or high temperature resistant polymer microspheres surface-coated with a functionalized polymer layer containing polar groups.
18. The coated modified composite separator according to embodiment 15, characterized in that the inorganic hybrid high temperature resistant polymer microspheres include at least one of polyimide/silica microspheres, polyimide/titanium dioxide microspheres, polyimide/zirconia microspheres, polyimide/zinc oxide microspheres, polyimide/magnesium oxide microspheres, polyimide/magnesium hydroxide microspheres, polyimide/boehmite microspheres.
19. The coated modified composite separator according to any one of embodiments 10 to 13, characterized in that the inorganic particles in the coating include at least one of ceramics, metal oxides, metal hydroxides, metal carbonates, silicates, kaolin, talc, minerals, and glass; preferably at least one of boehmite, alumina, silica, barium titanate, titanium dioxide, zinc oxide, magnesium oxide, magnesium hydroxide, zirconia or an oxide solid electrolyte;
20. The coated modified composite separator according to any one of embodiments 11 to 14, characterized in that the coating further comprises at least one of a binder, a surfactant, a dispersant, a wetting agent, and a defoaming agent;
21. The coated modified composite separator according to embodiment 1, characterized in that the coating comprises high temperature resistant polymer nanofibers and inorganic particles, and the weight ratio of the high temperature resistant polymer nanofibers to inorganic particles is (0.4-65):(99.6-35).
22. The coated modified composite separator according to embodiment 21, wherein the weight ratio of high temperature resistant polymer nanofibers to inorganic particles in the coating is (1-64):(99-36), preferably (3-62):(97-38), most preferably (5-59):(95-41).
23. The coated modified composite separator according to either one of embodiments 21-22, wherein the base membrane is at least one of a polymer base membrane and a base membrane coated with inorganic particles;
24. The coated modified composite separator according to any one of embodiments 21 to 23, the polymer base membrane includes a single-layer membrane, a double-layer membrane or a multi-layer membrane, and the polymer base membrane contained in each layer are the same or different.
25. The coated modified composite separator according to any one of embodiments 21 to 24, wherein the high temperature resistant polymer nanofibers include at least one of the following: unmodified high temperature resistant polymer nanofibers, surface modified high temperature resistant polymer nanofibers, and inorganic hybrid high temperature resistant polymer nanofibers.
26. The coated modified composite separator according to any one of embodiments 21 to 25, wherein the diameter of the high temperature resistant polymer nanofibers is 5-1500 nm, preferably 6-1450 nm, and more preferably 8-1350 nm; and/or the length of the high temperature resistant polymer nanofibers is 0.5-1000 μm, preferably 0.6-950 μm, and more preferably 1.0-900 μm.
27. The coated modified composite separator according to any one of embodiments 21 to 26, wherein the unmodified high temperature resistant polymer nanofibers and the high temperature-resistant polymer nanofibers used for surface modification and inorganic hybridization include at least one of: P84 nanofibers, polyetherimide nanofibers, polyvinylidene fluoride and its copolymer nanofibers, polyvinylidene fluoride-hexafluoropropylene nanofibers, polytetrafluoroethylene nanofibers, polyphosphazene nanofibers, polyacrylonitrile nanofibers, polyimide nanofibers, polyester nanofibers, cellulose nanofibers, polyether ether ketone nanofibers, polyaryl ether nanofibers, polyamide nanofibers, and polybenzimidazole nanofibers.
28. The coated modified composite separator according to any one of embodiments 21 to 27, wherein the surface modified high temperature resistant polymer nanofibers include at least one of inorganic surface-modified high temperature resistant polymer nanofibers, high temperature resistant polymer nanofibers with polar groups after surface treating, or high temperature resistant polymer nanofibers surface-coated with a functionalized polymer layer containing polar groups.
29. The coated modified composite separator according to any one of embodiments 21 to 28, characterized in that the inorganic particles in the coating include at least one of ceramics, metal oxides, metal hydroxides, metal carbonates, silicates, kaolin, talc, minerals, and glass; preferably at least one of boehmite, alumina, silica, barium titanate, titanium dioxide, zinc oxide, magnesium oxide, magnesium hydroxide, zirconia or an oxide solid electrolyte;
30. The coated modified composite separator according to any one of embodiments 21 to 29, wherein the coating further comprises at least one of a binder, a surfactant, a dispersant, a wetting agent, and a defoaming agent.
31. The coated modified composite separator according to any one of embodiments 21-30, wherein the amount of the binder is 0.5-12.5 parts by weight, preferably 0.6-12 parts by weight, more preferably 1.0-9 parts by weight; and/or
32. A preparation method of the coated modified composite separator according to any one of embodiments 21 to 30, characterized in that it includes the following steps:
33. The preparation method according to embodiment 32, the coating slurry comprises high temperature resistant polymer microspheres and high temperature resistant polymer nanofibers, wherein the high temperature resistant polymer is polyimide, the method includes the following steps:
34. The preparation method according to embodiment 33, characterized in that, for the polyamic acid solution used in step A, the dianhydride is one or a mixture of two or more of pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,3,3′,4′-biphenyltetracarboxylic dianhydride (α-BPDA), 4,4′-diphenyl ether dianhydride (ODPA), 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA), hexafluorodianhydride (6FDA), bisphenol A diether dianhydride (BPADA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydrides (DSDA), the diamine is one or a mixture of two or more of 4,4′-diaminodiphenyl ether (ODA), p-phenylenediamine (p-PDA), 3,4′-diaminodiphenylmethane (3,4′-MDA), 4,4′-diaminodiphenylmethane (4,4′-MDA), 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFMB), 1,3-bis(4-aminophenoxy)benzene (1,3,4-APB), 2,2′-bis(trifluoromethyl)-4,4′-diaminophenyl ether (6FODA), 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP), 2,2-bis [4-(4-aminophenoxy)phenyl]propane (BAPP); or is prepared by blending at least two polyamic acid solutions; the solid content of the polyamic acid solution is 5-40 wt %; the electrospinning parameters are as following: the spinning voltage 15-100kV, preferably 16-80kV, more preferably 17-75 kV, or 15-55 kV, and the receiving distance 10-30 cm.
35. The preparation method according to embodiment 33, characterized in that the thermal imidization process used in step B has a maximum temperature of 250-450° C., preferably 300-450° C., and a residence time of 0.1-30 min, or 1-30 min.
36. The preparation method according to embodiment 33, characterized in that the binder in step C is one or more of an aqueous PVDF emulsion, polyvinyl alcohol, polyethylene oxide, an acrylic water-soluble glue, styrene-butadiene rubber, sodium carboxymethylcellulose and polyvinylpyrrolidone; the weight parts of each component of the coating slurry are as following: 1-3 parts of binder, 89-52 parts of solvent, and 10-45 parts of polyimide; the dispersion liquid is water.
37. The preparation method according to embodiment 33, characterized in that in step D, the polyolefin separator is coated with polyimide on one side or both sides, and the coating method is one of electrostatic spraying, blade coating, extrusion coating, transfer coating, wire rod coating, dip coating, gravure or micro-gravure coating.
38. The preparation method according to embodiment 32, the coating slurry comprises high temperature resistant polymer microspheres or high temperature resistant polymer microspheres and inorganic particles, characterized in that the preparation method includes the following steps:
39. The preparation method according to embodiment 38, characterized in that the solid content of the coating slurry is 2-71.4 wt %, preferably 4-70 wt %, and more preferably 10-62 wt %;
40. The preparation method according to any one of embodiments 38-39, characterized in that the slurry solvent is one of water type solvent or organic solvent,
41. The preparation method according to any one of embodiments 38-39, characterized in that the coating method of the coating includes at least one of electrostatic spraying, blade coating, rotating spraying, extrusion coating, transfer coating, dip coating, wire rod coating, gravure or micro-gravure coating.
42. The preparation method according to embodiment 32, characterized in that the coating slurry comprises high temperature resistant polymer nanofibers and inorganic particles, and the method includes the following steps:
43. The preparation method according to embodiment 42, wherein the coating slurry comprises the following components by weight: 0.4-65 parts of high temperature resistant polymer nanofibers, 35-99.6 parts of inorganic particles, 100-5000 parts of slurry solvent; the sum of the weight parts of high temperature resistant polymer nanofibers and inorganic particles is 100.
44. The preparation method according to any one of embodiments 42-43, wherein the solid content of the coating slurry is 2-50 wt %, preferably 6-48 wt %, more preferably 10-43 wt %; and/or
45. The preparation method according to any one of embodiments 42-44, wherein the slurry solvent is one of water type solvent or organic solvent,
46. The preparation method according to any one of embodiments 42-43, the coating slurry further comprises an additive selected from at least one of a binder, a surfactant, a dispersant, a wetting agent, a defoaming agent and the like.
47. The preparation method according to any one of embodiments 42-44, wherein the amount of slurry solvent is 100-5000 parts by weight, preferably 120-4000 parts by weight, and most preferably 150-2900 parts by weight; and/or
48. The preparation method according to any one of embodiments 42 to 45, wherein the coating method of the coating includes at least one of electrostatic spraying, blade coating, rotating spraying, extrusion coating, transfer coating, dip coating, wire rod coating, gravure or micro-gravure coating.
49. A coating slurry comprising a slurry solvent and at least two of the following:
50. The coating slurry according to embodiment 49, characterized in that it comprises high temperature resistant polymer nanofibers, inorganic particles and the slurry solvent, wherein the high temperature resistant polymer nanofibers are 0.4-65 parts by weight, the inorganic particles are 35-99.6 parts by weight parts, and the sum of the weight parts of high temperature resistant polymer nanofibers and inorganic particles is 100.
51. The coating slurry according to any one of embodiments 49-50, wherein the solid content of the coating slurry is 2-50 wt %, preferably 6-48 wt %, more preferably 10-43 wt %; and/or
52. The coating slurry according to any one of embodiments 49 to 50, wherein the slurry solvent is one of water type solvent or organic solvent,
53. The coating slurry according to any one of embodiments 49-51, the coating slurry further comprises an additive selected from at least one of a binder, a surfactant, a dispersant, a wetting agent, a defoaming agent and the like.
54. The coating slurry according to any one of embodiments 49-51, wherein the amount of slurry solvent is 100-5000 parts by weight, preferably 120-4000 parts by weight, and most preferably 150-2900 parts by weight; and/or
55. A lithium ion battery, characterized in that the lithium ion battery includes a positive electrode, a negative electrode, an electrolyte and a separator, wherein the separator is the coated modified composite separator according to any one of embodiments 1-31 or the coated modified composite separator prepared by the method according to any one of embodiments 32-48.
56. A coated modified composite separator, characterized in that,
57. A preparation method of the coated modified composite separator according to embodiment 56, characterized in that it includes the following steps:
58. A coating slurry, comprising a slurry solvent, high temperature resistant polymer nanofibers and at least one of:
59. A coated modified composite separator, characterized in that,
60. A preparation method of the coated modified composite separator according to embodiment 59, characterized in that it includes the following steps:
61. A coating slurry, comprising a slurry solvent and:
The endpoints and any values of ranges disclosed herein are not limited to the precise ranges or values, but these ranges or values are to be understood to include values near such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges shall be deemed as being specifically disclosed herein.
The foregoing descriptions of embodiments have been presented for purposes of illustration and description. It is not intended to be exhaustive or limit the present disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in other selected embodiments, even if not expressly shown or described. It can also be modified in many ways. Such modifications should not be considered a departure from the present disclosure, and all such modifications are intended to be included within the scope of present application.
There are no particularly limited of the types of the base membrane in present application, and it can be any type of base membrane; the base membrane is a polymer base membrane or a base membrane coated with inorganic particles, such as a ceramic base membrane, and the ceramic base membrane is the same as conventional ceramic base membranes referred to in this field, including both a polymer base membrane and a ceramic layer coated on at least one side of the polymer base membrane. In some embodiments, the thickness of the base membrane is 1.5-40 μm; preferably 2.0-35 μm, more preferably 3.5-30 μm. The thickness of the base membrane is preferably 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, 7 μm or more, 9 μm or more, or 12 μm or more, and the thickness of the base membrane is preferably 37 μm or less, 35 μm or less, 33 μm or less, 30 μm or less, 28 μm or less, or 26 μm or less.
Examples of the polymer base membrane include, but not limited to, at least one of polyolefin base membrane, cellulose base membrane, polyester base membrane, aramid base membrane, polyimide base membrane, and organic-inorganic hybrid base membrane. In some embodiments, the polymer base membrane includes a single-layer membrane, a double-layer membrane or a multi-layer membrane, and the polymer base membrane contained in each layer can be the same or different. In some embodiments, for a double-layer polyer membrane or a multi-layer polymer base membrane, the thickness of each layer may be same as or different from that of other layers. In some embodiments, for a double-layer polymer base membrane or a multi-layer polymer base membrane, each layer may be prepared by using same or different processes, such as co-extruding and/or laminating together. In some embodiments, the polymer base membrane includes a polyolefin base membrane, and the polyolefin can include, but not limited to polyethylene, polypropylene, polybutylene, copolymers of above polyolefins, and blends thereof.
In some embodiments, the polyolefin can be an ultra-low molecular weight, low molecular weight, medium molecular weight, high molecular weight, or ultra-high molecular weight polyolefin. For example, the ultra-high molecular weight polyolefin may have a molecular weight of 450,000 (450k) or higher, such as 500k or more, 600k or more, 700k or more, 800k or more, 1 million or more, 2 million or more, 3 million or more, etc. The high molecular weight polyolefin may have a molecular weight in the range of 250k to 450k, such as 250k to 400k, 250k to 350k or 250k to 300k. The medium molecular weight polyolefin may have a molecular weight of 150 to 250k, such as 150k to 225k, 150k to 200k, 150k to 200k, etc. The low molecular weight polyolefin may have a molecular weight in the range of 100k to 150k, such as 100k to 125k. The ultra-low molecular weight polyolefin may have a molecular weight of less than 100k. The above numerical values are weight average molecular weights. The polyolefin separator may have the following non-limiting constructions: PP, PE, PP/PP, PP/PE, PE/PP, PE/PE, PE/PP/PE, etc.
According to the present invention, there are no special requirements for the inorganic particle coating, such as the ceramic layer, in the inorganic particle coated base membrane, and the ceramic layers commonly used in this field can be selected. Ceramic particles in the ceramic layer can include, but not limited to, at least one of Al2O3 (including α, β, γ types), SiO2, BaSO4, BaO, titanium dioxide (TiO2, rutile or anatase), CuO, MgO, Mg(OH)2, LiAlO2, ZrO2, carbon nanotubes (CNT), BN, SiC, Si3N4, WC, BC, AlN, Fe2O3, BaTiO3, MoS2, V2O5, PbTiO3, TiB2, CaSiO3, molecular sieve (ZSM-5), clay, boehmite and kaolin, preferably at least one of Al2O3, SiO2 and BaSO4.
The separators disclosed in the present invention can additionally contain a filler, an elastomer, a wetting agent, a lubricant, a flame retardant, a nucleating agent, an antioxidant, a colorant and/or other additional components not inconsistent with the objectives of the present invention. For example, the substrate can contain fillers such as calcium carbonate, zinc oxide, diatomaceous earth, talc, kaolin, synthetic silica, mica, clay, boron nitride, silicon dioxide, titanium dioxide, barium sulfate, aluminum hydroxide, magnesium hydroxide, etc., or combinations thereof. The elastomer may include ethylene-propylene (EPR), ethylene-propylene-diene (EPDM), styrene-butadiene (SBR), styrene isoprene (SIR), ethylidene norbornene (ENB), epoxy resin and polyurethane, or combinations thereof. The wetting agent may include ethoxylated alcohols, primary polymeric carboxylic acids, glycols (such as polypropylene glycol and polyethylene glycol), functionalized polyolefins, and the like. The lubricant may include silicones, fluoropolymers, oleamide, stearamide, erucamide, calcium stearate, lithium stearate, or other metal stearates. The flame retardant may include brominated flame retardants, ammonium phosphate, magnesium hydroxide, aluminum oxide trihydrate, and phosphate esters. The nucleating agent may include any nucleating agent that is not inconsistent with the objectives of the present invention.
The coating of the present invention comprises at least two of the following: high temperature resistant polymer microspheres, high temperature resistant polymer nanofibers, and inorganic particles.
In some embodiments, the thickness of the coating is 0.2-10 μm, and the thickness of the coating is preferably 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, 0.7 μm or more, 1 μm or more, or 1.2 μm or more, and the thickness of the coating layer is preferably 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, or 5 μm or less. If the thickness of the coating is lower than 0.2 μm, the thermal dimensional stability, electrolyte retention rate and capacity retention rate of the modified separator will be reduced; if the thickness of the coating is higher than 10 μm, the difficulty of coating will increase, and at the same time, the electrolyte retention rate of the electrolyte increases, resulting in a decrease in the energy density of the battery.
In some embodiments, the coating and/or coating slurry comprise high temperature resistant polymer nanofibers and inorganic particles. The coating comprises, in parts by weight, 0.4-65 parts of high temperature resistant polymer nanofibers, 35-99.6 parts of inorganic particles, and the sum of the weight parts of high temperature resistant polymer nanofibers and inorganic particles is 100. In some embodiments, the weight parts of the high temperature resistant polymer nanofibers in the coating is preferably 1-64, 2-63, 3-62, 4-61, 5-59 or 7-58. In some embodiments, the weight parts of inorganic particles in the coating is preferably 36-99, 37-98, 38-97, 39-96, 41-95, or 42-93.
In some embodiments, the coating and/or coating slurry comprise high temperature resistant polymer microspheres and inorganic particles. The coating comprises, in parts by weight, 0.1-100 parts of high temperature resistant polymer microspheres, 99.9-0 parts of inorganic particles, preferably 0.1-99.9 parts of high temperature resistant polymer microspheres, and 99.9-0.1 parts of inorganic particles, and the sum of the weight parts of high temperature resistant polymer microspheres and inorganic particles is 100. In some embodiments, the weight parts of high temperature resistant microspheres in the coating is preferably 0.3-100, 1-100, 3-100, 5-100, 7-100 or 10-100. In some embodiments, the weight parts of inorganic particles in the coating is preferably 99.7-0, 99-0, 97-0, 95-0, 93-0 or 90-0.
In some embodiments, the coating and/or coating slurry comprise high temperature resistant polymer microspheres, or high temperature resistant polymer microspheres and high temperature resistant polymer nanofibers.
In some embodiments, the coating and/or coating slurry comprise high temperature resistant polymer nanofibers, and at least one of high temperature resistant polymer microspheres and inorganic particles. In some embodiments, the coating and/or coating slurry comprise high temperature resistant polymer microspheres, high temperature resistant polymer nanofibers, and inorganic particles. The incorporation of high temperature resistant polymer nanofibers can form a network structure, increase the integrity of the coating, and can avoid the pulverizing problem of single component of microsphere structure caused by binder failure at high temperature.
In some embodiments, the coating slurry comprises high temperature resistant polymer microspheres and high temperature resistant polymer nanofibers, wherein the high temperature resistant polymer in the high temperature resistant polymer microspheres and high temperature resistant polymer nanofibers is polyimide. In above embodiments, the preparation method of the polyolefin composite separator modified by coating with polyimide includes the steps of:
For the polyamic acid solution used in step A, the dianhydride is one or a mixture of two or more of pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,3,3′,4′-biphenyltetracarboxylic dianhydride (α-BPDA), 4,4′-diphenyl ether dianhydride (ODPA), 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA), hexafluorodianhydride (6FDA), bisphenol A diether dianhydride (BPADA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydrides (DSDA), the diamine is one or a mixture of two or more of 4,4′-diaminodiphenyl ether (ODA), p-phenylenediamine (p-PDA), 3,4′-diaminodiphenylmethane (3,4′-MDA), 4,4′-diaminodiphenylmethane (4,4′-MDA), 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFMB), 1,3-bis(4-aminophenoxy)benzene (1,3,4-APB), 2,2′-bis(trifluoromethyl)-4,4′-diaminophenyl ether (6FODA), 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP), 2,2-bis [4-(4-aminophenoxy)phenyl]propane (BAPP); or is prepared by blending at least two polyamic acid solutions; the solid content of the polyamic acid solution is 5-40 wt %; the electrospinning parameters are as following: the spinning voltage 15-100kV, preferably 16-80kV, more preferably 17-75 kV, or 15-55 kV, and the receiving distance 10-30 cm.
The thermal imidization process used in step B has a maximum temperature of 250-450° C., preferably 300-450° C., and a residence time of 0.1-30 min, or 1-30 min.
The binder in step C is one or more of an aqueous PVDF emulsion, polyvinyl alcohol, polyethylene oxide, an acrylic water-soluble glue, styrene-butadiene rubber, sodium carboxymethylcellulose and polyvinylpyrrolidone; the weight parts of each component of the coating slurry are as following: 1-3 parts of binder, 89-52 parts of solvent, and 10-45 parts of polyimide; the dispersion liquid is water.
In step D, the polyolefin separator is coated with polyimide on one side or both sides, and the coating method is one of electrostatic spraying, blade coating, extrusion coating, transfer coating, wire rod coating, dip coating, and gravure or micro-gravure coating.
In some embodiments, the coating and/or coating slurry further comprise an additive selected from at least one of a binder, a surfactant, a dispersant, a wetting agent, a defoaming agent and the like.
The binder includes, but not limited to, at least one of polyvinylidene fluoride and its copolymers, polyvinyl alcohol, polyacrylates, styrene-butadiene rubber, carboxymethylcellulose and its salts, polyvinylpyrrolidone, and polyimide. The amount of the adhesive is 0.5-12.5 parts by weight. In some embodiments, the amount of binder is preferably 0.6-12, 0.7-11, 0.8-10 or 1.0-9 parts by weight.
The surfactant includes, but not limited to, at least one of fluorocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants, preferably perfluoroalkyl ether alcoholamine salts, perfluoroalkyl ether quaternary ammonium salts, potassium perfluoroalkyl ether carboxylate fluorocarbon surfactants, and polyethylene glycol type, polyol type, block copolyether and special polyether nonionic surfactants. The amount of the surfactant is 0.1-5 parts by weight. In some embodiments, the surfactant is preferably used in an amount of 0.2-4.9, 0.3-4.8, 0.4-4.7 or 0.6-4.5 parts by weight.
The dispersant includes, but not limited to at least one of tris(2-ethylhexyl) phosphate, sodium lauryl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyethylene glycol esters, and cellulose ethers, preferably hydroxypropyl methylcellulose or polyacrylamide. The amount of the dispersant is 0.1-7 parts by weight. In some embodiments, the dispersant is preferably used in an amount of 0.2-6.9, 0.3-6.8, 0.4-6.4 or 0.6-6.0 parts by weight.
The wetting agent includes, but not limited to, at least one of monohydric alcohols, dihydric alcohols and trihydric alcohols; preferably at least one of ethanol, ethylene glycol, glycerol, isopropyl alcohol and butanol. The amount of the wetting agent is 0.05-5 parts by weight. In some embodiments, the amount of the wetting agent is preferably 0.06-4.9, 0.07-4.8, 0.09-4.7 or 0.11-4.3 parts by weight.
The defoaming agent includes, but not limited to, at least one of alcohols, fatty acids and fatty acid esters, amides, phosphate esters, silicones, polyethers, and polyether-modified polysiloxanes defoaming agents; preferably at least one of monoalkyl, dialkyl phosphates and fluorinated alkyl phosphates and polyether-modified silicones defoaming agents. The amount of the defoaming agent is 0.1-4 parts by weight. In some embodiments, the amount of the defoaming agent is preferably 0.2-3.9, 0.3-3.7, 0.4-3.5 or 0.6-3.3 parts by weight.
The coating method of the coating is not particularly limited, including but not limited to at least one of electrostatic spraying, blade coating, rotating spraying, extrusion coating, transfer coating, dip coating, wire rod coating, gravure or micro-gravure coating; preferably extrusion coating, gravure coating, or micro-gravure coating.
In some embodiments, the base membrane coated with the coating slurry is dried. The drying temperature is 40-210° C., preferably 50-200° C.; and the drying time is 0.1-60 min, or 1-60 min, or 5-50 min. The drying method is preferably oven drying.
The high temperature resistant polymer microspheres include unmodified high temperature resistant polymer microspheres, surface modified high temperature resistant polymer microspheres, and/or inorganic hybrid high temperature resistant polymer microspheres.
The particle size of the high temperature resistant polymer microspheres is 3-20000 nm, preferably 5 nm or more, 7 nm or more, 9 nm or more, 12 nm or more, 15 nm or more, 20 nm or more, and preferably 50 nm or less, 11000 nm or less, 13000 nm or less, 15000 nm or less, or 18000 nm or less.
The preparation method of the high temperature resistant polymer microspheres is not subject to special limitations, and includes, but not limited to, at least one of electrostatic spraying method, phase separation method, template method, precipitation method, blowing method, blowing assisted electrospinning method, centrifugal method, self-assembly method, solution spinning method, in-situ synthesis method, and reprecipitation method. In some embodiments, electrostatic spraying method is used to prepare the high temperature resistant polymer microspheres. In the polymer solution used for electrostatic spraying, the concentration of the spinning polymer is 3-30 wt %, more preferably 8-20 wt %. When the relative molecular mass of the polymer is fixed and other conditions are constant, the concentration of the spinning solution is the decisive factor affecting the entanglement of the molecular chains in the solution.
The polymer in the unmodified high temperature resistant polymer microspheres, the surface modified high temperature resistant polymer microspheres and inorganic hybrid high temperature resistant polymer microspheres includes but not limited to at least one of P84, polyetherimide, polyphosphazene, polyacrylonitrile, polystyrene, polyvinylidene fluoride, polyvinylidene fluoride copolymer, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polytetrafluoroethylene, polyimide, polyester, cellulose, polyether ether ketone, polyarylether, polyamide, and polybenzimidazole.
Polyimide microspheres are preferred. The polyimide in the polyimide microspheres is prepared by homopolycondensation and copolycondensation of a raw material mixture containing polybasic acid anhydride and polyamine.
The surface modified high temperature resistant polymer microspheres include, but not limited to, inorganic surface-modified high temperature resistant polymer microspheres, high temperature resistant polymer microspheres with polar groups after surface treating, or high temperature resistant polymer microspheres surface-coated with a functionalized organic substance layer containing polar group(s). The polar group includes but not limited to at least one of hydroxyl, carboxyl, sulfonic acid group, amino, phosphate ester group, halogen, and nitro. The functionalized organic substance containing polar group(s) includes but not limited to polymers such as at least one of polyphosphazene, polyacrylonitrile, polyphosphoric acid, polysiloxane, polyester polymer, polyetherimide, polyether ether ketone, polyarylether and polybenzimidazole, and aromatic sulfonic acid derivatives such as 8-aminopyrene-1,3,6-trisulfonic acid and its salts. It should be noted that the above-mentioned surface modification is not grafting on original particles to prepare core-shell structure. Compared with core-shell structure particles, which are difficult and costly to prepare, the surface modification of the present invention is simpler in preparation, has fewer components, and has lower process cost.
The inorganic hybrid high temperature resistant polymer microspheres contain an inorganic substance. The inorganic substances used for surface modification and for inorganic hybrid high temperature resistant polymer microspheres include but not limited to at least one of alumina, boehmite, magnesium oxide, zirconia, barium titanate, titanium dioxide, silica, magnesium hydroxide, and zinc oxide.
The inorganic particles in the coating include, but not limited to at least one of ceramics, boehmite, metal oxides, metal hydroxides, metal carbonates, silicates, kaolin, talc, minerals, and glass. In some embodiments, the inorganic particles comprise at least one of boehmite, alumina, silica, barium titanate, titanium dioxide, zinc oxide, magnesium oxide, magnesium hydroxide, zirconia, or an oxide solid electrolyte. Further, the oxide solid electrolyte includes at least one of perovskite type, NASICON type, LISICON type, garnet type and LiPON type electrolyte.
The high temperature resistant polymer nanofibers include unmodified high temperature resistant polymer nanofibers, surface modified high temperature resistant polymer nanofibers, and/or inorganic hybrid high temperature resistant polymer nanofibers.
The diameter of the high temperature resistant polymer nanofibers is 5-1500 nm, preferably 6 nm or more, 7 nm or more, 8 nm or more, 10 nm or more, 15 nm or more, or 20 nm or more, and preferably 1450 nm or less, 1400 nm or less, 1350 nm or less, 1300 nm or less, or 1200 nm or less. The length of the high temperature resistant polymer nanofibers is 0.5-1000 μm, preferably 0.6 μm or more, 1.0 μm or more, 3.0 μm or more, 5.0 μm or more, 7.0 μm or more, or 10.0 μm or more, and preferably 950 μm or less, 900 μm or less, 800 μm or less, 700 μm or less, or 600 μm or less. The aspect ratio of the high temperature resistant polymer nanofibers is 5-2000, preferably 10-1500, more preferably 20-500.
The preparation method of the high temperature resistant polymer nanofibers is not subject to special limitations, and includes, but not limited to, at least one of electrospinning method, phase separation method, template method, precipitation method, blowing method, blowing assisted electrospinning method, centrifugal method, self-assembly method, solution spinning method, and in-situ synthesis method. In some embodiments, electrospinning method is used to prepare the high temperature resistant polymer nanofibers. In the polymer solution used for electrospinning method, the concentration of the spinning polymer is 3-30 wt %, more preferably 8-20 wt %. When the relative molecular mass of the polymer is fixed and other conditions are constant, the concentration of the spinning solution is the decisive factor affecting the entanglement of the molecular chains in the solution. In the present invention, when the concentration of the spinning solution is within the above range, the spinning performance can be effectively ensured. Moreover, as the concentration of the spinning solution increases, the degree of polymer entanglement increases, resulting in a better spinning performance. In the present invention, when electrospinning is performed by using spinning solutions containing different polymers, the concentration of each spinning solution is independently selected from the above concentration ranges.
The unmodified high temperature resistant polymer nanofibers, the surface modified high temperature resistant polymer nanofibers and inorganic hybrid high temperature resistant polymer nanofibers include but not limited to at least one of P84 nanofibers, polyetherimide nanofibers, polyvinylidene fluoride and its copolymer nanofibers, polyvinylidene fluoride-hexafluoropropylene nanofibers, polytetrafluoroethylene nanofibers, polyphosphazene nanofibers, polyacrylonitrile nanofibers, polyimide nanofibers, polyester nanofibers, cellulose nanofibers, polyether ether ketone nanofibers, polyaryl ether nanofibers, polyamide nanofibers, and polybenzimidazole nanofibers.
The polyimide in the polyimide nanofibers is prepared by homopolycondensation and copolycondensation of a raw material mixture containing polybasic acid anhydride and polyamine.
The surface modified high temperature resistant polymer nanofibers include, but not limited to, inorganic surface-modified high temperature resistant polymer nanofibers, high temperature resistant polymer nanofibers with polar groups after surface treating, or high temperature resistant polymer nanofibers surface-coated with a functionalized organic substance layer containing polar group(s). The polar group includes but not limited to at least one of hydroxyl, carboxyl, sulfonic acid group, amino, phosphate ester group, halogen, and nitro. Compounds used for surface treatment include but not limited to oxidants such as potassium permanganate, chlorate, potassium dichromate and the like, acidic compounds such as sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid and the like, alkaline compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, barium hydroxide, strontium hydroxide, rubidium hydroxide, aqueous ammonia, methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, triethylamine, hydrazine hydrate, DMAB, salts of strong base and weak acid and the like. The functionalized organic substance containing polar group(s) includes but not limited to polymers such as at least one of polyphosphazene, polyacrylonitrile, polyphosphoric acid, polysiloxane, polyester polymer, polyetherimide, polyether ether ketone, polyarylether and polybenzimidazole, and aromatic sulfonic acid derivatives such as 8-aminopyrene-1,3,6-trisulfonic acid and its salts.
The inorganic hybrid high temperature resistant polymer nanofibers contain an inorganic substance. The inorganic substances used for surface modification and used for inorganic hybrid high temperature resistant polymer nanofibers include but not limited to at least one of alumina, boehmite, magnesium oxide, zirconia, barium titanate, titanium dioxide, silica, magnesium hydroxide, and zinc oxide.
In the coating according to the present invention, the inorganic particles are selected from inorganic particles commonly used in this field. The inorganic particles in the coating include, but not limited to, at least one of ceramics, metal oxides, metal hydroxides, metal carbonates, silicates, kaolin, talc, minerals, and glass. In some embodiments, inorganic particles in the coating include, but not limited to, at least one of Al2O3 (including α, β, γ types), SiO2, BaSO4, BaO, titanium dioxide (TiO2, rutile or anatase), CuO, MgO, Mg(OH)2, LiAlO2, ZrO2, BN, SiC, Si3N4, WC, BC, AlN, Fe2O3, BaTiO3, MOS2, V2O5, PbTiO3, TiB2, CaSiO3, molecular sieve (ZSM-5), clay, boehmite and kaolin, preferably using at least one of Al2O3, boehmite, MgO, Mg(OH)2, titanium dioxide (TiO2, rutile or anatase), SiO2 and BaSO4. In some embodiments, the inorganic particles include at least one of boehmite, alumina, silica, barium titanate, titanium dioxide, zinc oxide, magnesium oxide, magnesium hydroxide, zirconia, or an oxide solid electrolyte. Further, the oxide solid electrolyte includes at least one of perovskite type, NASICON type, LISICON type, garnet type and LiPON type electrolyte.
The average particle size of the inorganic particles is 10 nm-5 μm, preferably 11 nm or more, 13 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, or 30 nm or more, and preferably 4.9 μm or less, 4.7 μm or less, 4.5 μm or less, 4.3 μm or less or 4.0 μm or less. In some embodiments, the inorganic particles have an average particle size of 10 nm-5 μm, preferably 11 nm-4.9 μm, and most preferably 15 nm-4.5 μm.
The present invention further provides a lithium ion battery, which includes a positive electrode, a negative electrode, an electrolyte and a separator, wherein the separator is said coated modified composite separator.
The positive electrode is made of a positive electrode material for lithium-ion battery, a conductive agent and a binder. The positive electrode materials used include any positive electrode materials that can be used in lithium-ion batteries, such as lithium cobaltate (LiCoO2), lithium nickelate (LiNiO2), lithium manganate (LiMn2O4), lithium iron phosphate (LiFePO4), lithium iron manganese phosphate (LiFexMn1-xPO4), lithium nickel-cobalt-manganate (LiNi1-x-yCoyMnxO2), lithium nickel-cobalt-aluminate (LiNi1-x-yCoyAlxO2e) and the like.
The negative electrode is made of a negative electrode material for lithium-ion battery, a conductive agent and a binder. The negative electrode materials used include any negative electrode materials that can be used in lithium-ion batteries, such as at least one of graphite, soft carbon, hard carbon, silicon carbon, silicon oxide carbon and the like.
The binder includes but not limited to at least one of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, polyamic acid, polyimide, aramid fiber and the like.
The conductive material is used to improve the conductivity of the electrodes, including but not limited to at least one of natural graphite, artificial graphite, carbon black, carbon fiber, carbon nanotube, graphene, carbon nanofiber, metal powder, metal fiber and the like. As the metal powder and metal fiber, metal copper, nickel, aluminum, silver and the like can be used.
The main improvement of the lithium-ion battery provided by the present invention is the using of the above-mentioned coated modified composite separator, and the arrangement (connection mode) of the positive electrode, negative electrode, separator and electrolyte can be the same as the prior art, which is known to those skilled in the art and will not be elaborated herein.
The preparation method of the lithium-ion battery provided by the present invention includes stacking or winding the positive electrode, the separator and the negative electrode in sequence into a cell, and then infusing the electrolyte into the cell and sealing, wherein the separator is said coated modified composite separator.
In order to make the purpose, technical solutions and advantages of the examples of the present invention clearer, the technical solutions in the examples of the present invention will be clearly and completely described below with reference to the figures in the examples of the present invention. Apparently, the described examples are a part of examples of the present invention, not all examples. Based on the examples of the present invention, all other examples obtained by those skilled in the art without creative work fall within the pretection scope of the present invention.
In the following examples of the present invention, the abbreviation C represents inorganic particles, the abbreviation P represents high temperature resistant polymer nanofibers and/or microspheres, and the abbreviation CP represents the composite of inorganic particles and high temperature resistant polymer nanofibers and/or microspheres.
The number in front of the abbreviation represents the coating thickness, for example, 4C represents an inorganic coating with a thickness of 4 μm, and 4CP represents a composite coating of inorganic particles and high temperature resistant polymer nanofibers and/or microspheres with a thickness of 4 μm.
The coating thickness in the examples of the present invention refers to the thickness after drying.
The modified composite separator is cut into a 5 cm×5 cm size separator and placed in an oven, and is kept at 150° C. or 200° C. for 30 minutes. The method for testing the thermal shrinkage rate refers to Chinese standard GB/T 36363-2018. The thermal shrinkage rate of the separator is measured in the longitudinal direction (MD) and transverse direction (TD), and then the higher value of the thermal shrinkage rate in MD and TD is defined as the thermal shrinkage rate of the separator.
The method for measuring the tensile strength of modified composite separators is in accordance with Chinese standard GB/T 36363-2018. The measurement is made on a type 2 sample with a width of (15±0.1) mm at conditions of an initial distance between the clamps of (100±5) mm and a test speed of (250±10) mm/min, and the maximum strength value during the tensile process of the sample being taken as tensile strength to record and compare. The tensile strength is measured in the longitudinal direction (MD) and the transverse direction (TD) respectively, and then the lower value of the tensile strength in MD and TD is defined as the tensile strength of the modified composite separator.
Wherein, the 200° C. tensile strength refers to the tensile strength tested according to the above method of samples cutted from the modified composite separator after it is maintained at 200° C. for 30 minutes and tested for heat shrinkage rate.
The method for measuring the air permeability of modified composite separators is in accordance with Chinese standard of GB/T 36363-2018. 3 pieces of modified composite separators with a size of 100 mm*100 mm are taken for the measurement. The modified composite separator is placed in a BTY-B2P type air permeability tester of Labthink Company for air permeability testing. Take the average value of the three test results as the air permeability of the modified composite separators.
A modified composite separator is cut into a 2 cm×2 cm square sample. The mass of a sample is weighed as Wa, and it is then put into a vacuum oven and heated at 60° C. for 2 hours to remove water. The dried fiber membrane after drying is completely soaked in n-butanol for at least 2 hours. The solvent on the membrane surface is completed absorbed through a filter paper. The mass of the membrane is then weighed as Wb. The porosity is calculated by using the following formula:
In the formula: ρp: density of the modified composite separator
A modified composite separator is cut into discs of corresponding specifications. Their thicknesses are measured. It is placed into a vacuum oven with the temperature being set to 80° C., and kept at the temperature for 10 hours. The assembly of a button battery is performed in a glove box, with the atmosphere in the box being argon and the sequence of shell, gasket, separator containing electrolyte, gasket, shell. After the battery is installed, let it stand for 12 hours. AC impedance is measured with a chemical workstation. Its amplitude is set to 5 mV, the time is 2 s, and the test range is 1-105 Hz. The internal resistance Rd of the separator can be obtained from the AC impedance diagram, and the ionic conductivity can be calculated according to the formula:
A full battery is made by using nickel-rich 8 series NCM ternary material (S85E) and a negative electrode silicon oxide carbon 450: the mass ratio of positive electrode plate mass proportion active material (S85E): adhesive (PVDF): conductive agent (SP)=95:1.8:3.2, solid content is 65 wt %, solvent is NMP; negative electrode plate mass proportion active material (silicon oxide carbon 450): binder (SBR: CMC=2.5:1.5): conductive agent (SP)=95:4.0:1.0, the solid content is 45 wt %, and the solvent is water. A 2Ah soft-packed laminated battery is made with the above electrode plates, and is performed a cycle test at 1C, with the ratio of the discharge capacity of the 100th cycle to the discharge capacity of the first cycle as the capacity retention rate.
Preparation of PMDA/ODA system polyimide (PI) with fiber/microsphere composite morphology: the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1 and reacted in the solvent N,N-dimethylformamide (DMF) in a 0° C. ice-water bath for 10 hours to obtain a clear and transparent polyamic acid solution with a mass concentration of 12%. The polyamic acid solution was electrospinned in an electric field with an electric field intensity of 1 kV/cm. A polyamic acid film was collected through a stainless steel drum, and then the polyamic acid film was peeled off from the drum and placed in a high-temperature furnace for imidization treatment. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining at 300° C. for 1 hour, opening the heating furnace, and naturally cooling to room temperature.
Formulating a coating slurry: a polymer binder, a mixed solvent of water and ethanol, and the polyimide film were mixed in a weight ratio of 1:79:20 to prepare the coating slurry. First, 0.8 g of the polyimide film was weighed and dispersed in 3.16 g of a mixed solvent of water and ethanol to obtain a polyimide dispersion. Then, 0.04 g CMC was weighted and added to the polyimide dispersion, stirring with a high-speed homogenizer at a rotation speed of 1000 rpm for 10 minutes.
Coating: the stirred PI slurry was put into a vacuum oven for 1 hour for defoaming treatment. The slurry was then evenly coated on one side of a PE separator and a single-sided ceramic PE separator using microgravure coating. The thicknesses of the base membrane were 7 and 7+2 μm, respectively marked as 7 and 7+2C. After coating, the thickness of the coating was 3 μm, and the membrane thicknesses were 10 and 12 μm, respectively marked as 7+3P and 7+2C+3P.
Drying: the separator coated with PI slurry was placed in a constant temperature oven to dry. The drying temperature was 50-100° C. and the drying time was 0.5 h-12 h. The obtained polyimide with fiber/microsphere composite morphology is shown in
After maintaining at 150° C. for 30 minutes, the heat shrinkage rate of the PE base membrane was 85%, the heat shrinkage rate of the PE/PI composite membrane was 4%; the heat shrinkage rate of the single-sided ceramic PE separator was 6%, and the heat shrinkage rate of the PI/PE/ceramic composite membrane was 0%.
After maintaining at 200° C. for 30 minutes, the heat shrinkage rate of the PE base membrane was 87%, the heat shrinkage rate of the PE/PI composite membrane was 4.5%; the heat shrinkage rate of the single-sided ceramic PE separator was 7%, and the heat shrinkage rate of the PI/PE/ceramic composite membrane was 0%.
Preparation of PMDA/4,4′-MDA system polyimide with fiber/microsphere composite morphology: the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (MDA) were weighed at a molar ratio of 1:1 and reacted in the solvent N,N-dimethylformamide (DMF) in a 0° C. ice-water bath for 10 hours to obtain a clear and transparent polyamic acid solution with a mass concentration of 12%. The polyamic acid solution was electrospinned in an electric field with an electric field intensity of 1 kV/cm. A polyamic acid film was collected through a stainless steel drum, and then the polyamic acid film was peeled off from the drum and placed in a high-temperature furnace for imidization treatment. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining at 300° C. for 1 hour, opening the heating furnace, and naturally cooling to room temperature.
Formulating a coating slurry: a polymer binder, a mixed solvent of water and ethanol, and the polyimide film were mixed in a weight ratio of 1:79:20 to prepare the coating slurry. First, 0.8 g of the polyimide film was weighed and dispersed in 3.16 g of a mixed solvent of water and ethanol to obtain a polyimide dispersion. Then, 0.04 g CMC was weighted and added to the polyimide dispersion, stirring with a high-speed homogenizer at a rotation speed of 1000 rpm for 10 minutes.
Coating: the stirred PI slurry was put into a vacuum oven for 1 hour for defoaming treatment. The slurry was then evenly coated on one side of a PE separator and a single-sided ceramic PE separator using microgravure coating.
Drying: the separator coated with PI slurry was placed in a constant temperature oven to dry. The drying temperature was 50-100° C. and the drying time was 0.5 h-12 h. The thicknesses of the base membrane were 7 and 7+2 μm, respectively marked as 7 and 7+2C. After coating, the thickness of the coating was 3 μm, and the membrane thicknesses were 10 and 12 μm, respectively marked as 7+3P and 7+2C+3P. The obtained polyimide with fiber/microsphere composite morphology is shown in
After maintaining at 150° C. for 30 minutes, the heat shrinkage rate of the PE base membrane was 85%, the heat shrinkage rate of the PE/PI composite membrane was 3.5%; the heat shrinkage rate of the single-sided ceramic PE separator was 6%, and the heat shrinkage rate of the PI/PE/ceramic composite membrane was 0%.
After maintaining at 200° C. for 30 minutes, the heat shrinkage rate of the PE base membrane was 87%, the heat shrinkage rate of the PE/PI composite membrane was 4%; the heat shrinkage rate of the single-sided ceramic PE separator was 7%, and the heat shrinkage rate of the PI/PE/ceramic composite membrane was 0%.
Preparation of PMDA/p-PDA system polyimide with fiber/microsphere composite morphology: the monomer pyromellitic dianhydride (PMDA) and the monomer p-phenylenediamine (p-PDA) were weighed at a molar ratio of 1:1 and reacted in the solvent N,N-dimethylformamide (DMF) in a 0° C. ice-water bath for 10 hours to obtain a clear and transparent polyamic acid solution with a mass concentration of 12%. The polyamic acid solution was electrospinned in an electric field with an electric field intensity of 1 kV/cm. A polyamic acid film was collected through a stainless steel drum, and then the polyamic acid film was peeled off from the drum and placed in a high-temperature furnace for imidization treatment. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining at 300° C. for 1 hour, opening the heating furnace, and naturally cooling to room temperature.
Formulating a coating slurry: a polymer binder, a mixed solvent of water and ethanol, and the polyimide film were mixed in a weight ratio of 1:79:20 to prepare the coating slurry. First, 0.8 g of the polyimide film was weighed and dispersed in 3.16 g of a mixed solvent of water and ethanol to obtain a polyimide dispersion. Then, 0.04 g CMC was weighted and added to the polyimide dispersion, stirring with a high-speed homogenizer at a rotation speed of 1000 rpm for 10 minutes.
Coating: the stirred PI slurry was put into a vacuum oven for 1 hour for defoaming treatment. The slurry was then evenly coated on one side of a PE separator and a single-sided ceramic PE separator using microgravure coating.
Drying: the separator coated with PI slurry was placed in a constant temperature oven to dry. The drying temperature was 50-100° C. and the drying time was 0.5 h-12 h. The thicknesses of the base membrane were 7 and 7+2 μm, respectively marked as 7 and 7+2C. After coating, the thickness of the coating was 3 μm, and the membrane thicknesses were 10 and 12 μm, respectively marked as 7+3P and 7+2C+3P. The obtained polyimide with fiber/microsphere composite morphology is shown in
After maintaining at 150° C. for 30 minutes, the heat shrinkage rate of the PE base membrane was 85%, the heat shrinkage rate of the PE/PI composite membrane was 3%; the heat shrinkage rate of the single-sided ceramic PE separator was 6%, and the heat shrinkage rate of the PI/PE/ceramic composite membrane was 0%.
After maintaining at 200° C. for 30 minutes, the heat shrinkage rate of the PE base membrane was 87%, the heat shrinkage rate of the PE/PI composite membrane was 3.2%; the heat shrinkage rate of the single-sided ceramic PE separator was 7%, and the heat shrinkage rate of the PI/PE/ceramic composite membrane was 0%.
(1) the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, and reacted in the solvent N,N-dimethylformamide (DMF) to obtain a clear and transparent polyamic acid solution with a mass concentration of 6%. PAA microspheres were prepared therefrom using electrostatic spraying method. The obtained microspheres were subjected to imidization treatment in a high temperature furnace. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour and obtaining polyimide microspheres.
(2) 10 g of polyimide microspheres (average particle size 800 nm), 90 g of ceramics, 1.5 g of a binder sodium carboxymethyl cellulose, 200 g of a mixed solvent of water and ethanol (ethanol 5 wt %), 0.3 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 0.3 g of a dispersant hydroxypropylmethylcellulose, 0.06 g of a wetting agent glycerol, 0.3 g of a defoaming agent fluorinated alkyl phosphate were weighed; the components were solved and evenly dispersed through stirring, to obtain a coating slurry.
(3) the stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on one side or both sides of a 7 μm polyethylene separator using microgravure coating to obtain coated polyethylene separators, marked as 7+4CP and 7+4CP+4CP; the non-ceramic side of the 7+4 μm single-sided ceramic polyethylene separator, marked as 7+4C+4P, which indicates a base membrane thickness of 7 μm and a ceramic coating thickness of 4 μm, the coating thickness obtained from the coating slurry from (2) of 4 μm.
(4) Drying: the coated polyethylene separators were placed in a constant temperature oven to dry. The drying temperature was 60° C. and the drying time was 0.5 h. The morphology of the obtained modified composite polyethylene separator is shown in
The above separators were tested for performance respectively, and the results are shown in Table 1 below:
(1) the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, and reacted in the solvent N,N-dimethylformamide (DMF) to obtain a clear and transparent polyamic acid solution with a mass concentration of 20%. Polyamic acid microspheres were prepared therefrom by blowing electrostatic spraying method. The microspheres were subjected to imidization treatment in a high temperature furnace. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour and obtaining polyimide microspheres.
(2) 80 g of boehmite, 20 g of polyimide microspheres (average particle size of microspheres: 200 nm), and 6.4 g of PVDF were weighed and dispersed in 450 g of NMP to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on one side or both sides of a 12 μm polypropylene separator using microgravure coating to obtain two types of coated polypropylene separators.
(4) The coated polypropylene separators were placed in a constant temperature oven to dry. The drying temperature was 60° C. and the drying time was 1 hour. The modified composite separators coated on one side and both sides obtained in step (3) were marked as 12+3CP and 12+3CP+3CP respectively. The non-ceramic side of a 12+3 μm single-sided ceramic polypropylene separator was evenly coated with the coating method according to step (3), marked as 12+3C+3CP, which indicates the base membrane thickness of 12 μm, the ceramic coating thickness of 3 μm, and the thickness of the coating obtained from the coating slurry of (2) of 3 μm.
The above separators were tested for performance respectively, and the results are shown in Table 2 below:
(1) The monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, added to the solvent N,N-dimethylformamide (DMF) and synthesized to obtain a clear and transparent polyamic acid solution (PAA) with a mass concentration of 10%, 100 nm LATP solid electrolyte was dispersed in a PAA solution to obtain a dispersion of LATP and polyamic acid. The dispersion was subjected to electrostatic spraying to obtain LATP/PAA hybrid microspheres. The microspheres were placed in a high-temperature furnace for imidization treatment. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour to obtain LATP/PI hybrid microspheres.
(2) 50 g of LATP/PI hybrid microspheres (average particle size of microspheres: 300 nm), 50 g of ceramics, 5.0 g of a binder PVDF, 390 g of a mixed solvent of water and ethanol (10 wt % ethanol), 2.5 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 2.5 g of a dispersant hydroxypropylmethylcellulose, and 0.1 g of a wetting agent glycerol were weighed and evenly stirred to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on both sides of a 7 μm polyethylene separator using extrusion coating to obtain a coated polyethylene separator.
(4) The coated polyethylene separator was placed in a constant temperature oven to dry. The drying temperature was 60° C. and the drying time was 1 hour. The separator was marked as 7+2CP+2CP.
The above separator was tested for performance, and the result is shown in Table 3 below:
(1) 7.3 g polyacrylonitrile was dissolved in 92.7 g N-methylpyrrolidone (NMP), and stirred to obtain a clear and transparent PAN solution with a mass concentration of 7.3%. PAN microspheres were prepared by blowing electrostatic spraying method.
(2) 5 g of PAN microspheres (average particle size of microspheres: 1000 nm) and 95 g of magnesium oxide were weighed and dispersed in 240 g of water, and stirred at high speed to obtain a PAN microspheres/magnesium oxide dispersion. Then 5.0 g of sodium carboxymethylcellulose was weighed and dissolved in 150 g of water to fully dissolve it. The above two slurries were mixed and stirred evenly to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on both sides of a 12 μm polypropylene separator using microgravure coating to obtain a coated polypropylene separator.
(4) The coated polypropylene separators were placed in a constant temperature oven to dry. The drying temperature was 60° C. and the drying time was 1 hour. The thickness of the dried coating was 3 μm and the separator was marked as 12+3CP+3CP.
The above separators were tested for performance respectively, and the results are shown in Table 4 below:
A Polyimide/Silica Microsphere/Li7La3Zr2O12 (LLZO) Garnet Type Solid Oxide Electrolyte Coated Polyethylene Separator
(1) 90 g of the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighted in a molar ratio of 1:1, and added to the solvent N,N-dimethylformamide (DMF) and synthesized to obtain a clear and transparent polyamic acid solution with a mass concentration of 12%. 10 g TEOS was added and stirred evenly. Polyamic acid microspheres were prepared therefrom by electrostatic spraying method. The microspheres were placed in a high-temperature furnace for imidization treatment. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining at 300° C. for 1 hour to obtain polyimide/silica microspheres, which contain silica on the surface and inside.
(2) 1 g of polyimide/silica microspheres (average particle size of microspheres: 1300 nm), 99 g of LLZO, 5 g of polyacrylamide, 1.8 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 0.5 g of a dispersant hydroxypropylmethylcellulose, 0.5 g of a wetting agent glycerol, and 0.2 g of a defoaming agent were solved in 140 g of water and sufficiently stirred to dissolve to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment. The slurry was then evenly coated on both sides of a 7 μm polyethylene separator using microgravure coating method.
(4) The coated polyethylene separator was placed in a constant temperature oven to dry. The drying temperature was 55° C. and the drying time was 0.5 hour.
The above separator was tested for performance, and the result is shown in Table 5 below:
(1) the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, and reacted in the solvent N,N-dimethylformamide (DMF) to obtain a clear and transparent polyamic acid solution with a mass concentration of 10%. Polyamic acid (PAA) microspheres were prepared therefrom by electrostatic blowing method. The temperature of the obtained microspheres was raised from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour to obtain polyimide microspheres.
(2) 20 g of polyimide microspheres (average particle size of the microspheres: 750 nm), 80 g of boehmite (average particle size of 500 nm), 1.5 g of sodium carboxymethylcellulose, 175 g of a mixed solvent of water and ethanol (ethanol 5 wt %), 0.3 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 0.3 g of a dispersant hydroxypropyl methylcellulose, 0.06 g of a wetting agent glycerol were weighed and stirred evenly to obtain a coating slurry.
(3) The coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on both sides of a 7 μm polyethylene separator using microgravure coating method to obtain a coated modified separator.
(4) The coated modified separator was placed in a constant temperature oven to dry. The drying temperature was 55° C. and the drying time was 1 hour. The obtained modified composite polyethylene separator was marked as 7+2CP+2CP.
The preparation process of Examples 2.7-2.14 was the same as that of Example 2.6, except that the inorganic particles and/or the high temperature resistant microspheres used in the coating were different.
The test results of test performance of Examples 2.6-2.14 are shown in Table 6.
(1) the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, and reacted in the solvent N,N-dimethylformamide (DMF) to obtain a polyamic acid solution with a mass concentration of 10%. Nano barium titanate (mass ratio of PAA:titanium dioxide of 95:5) was added thereto, stirred thoroughly. PAA hybrid microspheres were prepared therefrom by electrostatic spraying method. The obtained microspheres were subjected to imidization treatment in a high-temperature furnace. The temperature-raising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining at 300° C. for 1 hour to obtain polyimide/barium titanate microspheres.
Steps (2)-(4) were the same as those in Example 2.6 except that the inorganic particles were changed to barium titanate.
(1) 7.5 g polyetherimide was solved in 92.5 g N-methylpyrrolidone (NMP), stirred to obtain a polyetherimide solution with a mass concentration of 7.5%. Polyetherimide microspheres were prepared therefrom by electrostatic spraying method.
Steps (2)-(4) were the same as those in Example 2.6.
(1) 7.5 g polyacrylonitrile was solved in 92.5 g N-methylpyrrolidone (NMP), stirred to obtain a PAN solution with a mass concentration of 7.5%. Polyacrylonitrile microspheres were prepared therefrom by electrostatic spraying method.
Steps (2)-(4) were the same as those in Example 2.6.
(1) 7.5 g P84 was solved in 92.5 g N-methylpyrrolidone (NMP), stirred to obtain a P84 solution with a mass concentration of 7.5%. P84 microspheres were prepared therefrom by blowing spraying method.
Steps (2)-(4) were the same as those in Example 2.6.
(1) 7.5 g PET was solved in 92.5 g xylenol, stirred to obtain a PET solution with a mass concentration of 7.5%. PET microspheres were prepared therefrom with electrostatic spraying method.
Steps (2)-(4) were the same as those in Example 2.6.
(1) the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, and reacted in the solvent N,N-dimethylformamide (DMF) to obtain a polyamic acid solution with a mass concentration of 10%. PAA microspheres were prepared therefrom by electrostatic blowing method. The temperature of the obtained microspheres was raised from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour to obtain polyimide microspheres.
(2) 100 g of polyimide microspheres (average particle size of microspheres: 750 nm), 1.5 g of sodium carboxymethylcellulose, 175 g of a mixed solvent of water and ethanol (ethanol 5 wt %), 0.3 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 0.3 g of a dispersant hydroxypropylmethylcellulose, 0.06 g of a wetting agent glycerol were weighed and stirred evenly to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on both sides of a 7 μm polyethylene separator using microgravure coating method to obtain a coated modified separator.
(4) The coated modified separator was placed in a constant temperature oven to dry. The drying temperature was 55° C. and the drying time was 1 hour. The obtained modified composite polyethylene separator was marked as 7+2P+2P.
(1) The monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, and reacted in the solvent N,N-dimethylformamide (DMF) to obtain a polyamic acid solution with a mass concentration of 6% in the example. PAA nanofibers were prepared with electrospinning method. The obtained fibers were subjected to imidization treatment in a high temperature furnace. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour and obtaining polyimide nanofibers.
(2) 10 g of polyimide nanofibers (average diameter of fibers 800 nm, aspect ratio in the range of 10-200), 90 g of ceramics, 1.5 g of a binder sodium carboxymethyl cellulose, 200 g of a mixed solvent of water and ethanol (ethanol 5 wt %), 0.3 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 0.3 g of a dispersant hydroxypropylmethylcellulose, 0.06 g of a wetting agent glycerol, 0.3 g of a defoaming agent fluorinated alkyl phosphate were weighed; the components were solved and evenly dispersed through stirring, to obtain a coating slurry.
(3) the stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on respectively one side or both sides of a 7 μm polyethylene separator using microgravure coating method to obtain coated polyethylene separators, marked as 7+4CP and 7+4CP+4CP; the non-ceramic side of the 7+4 μm single-sided ceramic polyethylene separator was marked as 7+4C+4P. The thickness of the base membrane was 7 μm.
(4) Drying: the coated polyethylene separators were placed in a constant temperature oven to dry. The drying temperature was 60° C. and the drying time was 0.5 h. The morphology of the obtained modified composite polyethylene separator is shown in
The above separators were tested for performance respectively, and the results are shown in Table 8 below:
(1) the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, added to the solvent N,N-dimethylformamide (DMF) to synthesize and obtain a polyamic acid solution with a mass concentration of 20% in the example. Polyamic acid nanofibers were prepared by blowing electrospinning method. The nanofibers were subjected to imidization treatment in a high temperature furnace. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour to obtain polyimide nanofibers.
(2) 80 g of boehmite, 20 g of polyimide nanofibers (average diameter of the fibers 200 nm, aspect ratio in the range of 10-200), and 6.4 g of PVDF were weighed and dispersed in 450 g of NMP to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on respectively one side or both sides of a 12 μm polypropylene separator using microgravure coating method to obtain two types of coated polypropylene separators.
(4) The coated polypropylene separators were placed in a constant temperature oven to dry. The drying temperature was 60° C. and the drying time was 1 hour. The modified composite separators coated on one side and both sides obtained in step (3) were marked as 12+4CP and 12+4CP+4CP respectively. The non-ceramic side of a 12+4 μm single-sided ceramic polypropylene separator was evenly coated with the coating method according to step (3), marked as 12+4C+4CP, which indicates the base membrane thickness of 12 μm, the ceramic coating thickness of 4 μm, and the thickness of the coating obtained from the coating slurry of (2) of 4 μm.
The morphology of the obtained modified composite polypropylene separator coating is shown in
The above separators were tested for performance respectively, and the results are shown in Table 9 below:
(1) P84 was solved in the solvent N,N-dimethylacetamide (DMAc) to obtain a polyamic acid solution with a mass concentration of 10% in the example. 100 nm LATP solid electrolyte was dispersed in the P84 solution to obtain LATP and P84 dispersion. The dispersion was electrospuned to obtain LATP/P84 hybrid nanofibers.
(2) 50 g of LATP/P84 hybrid nanofibers (average diameter of the fibers: 300 nm, aspect ratio in the range of 20-400), 50 g of ceramics, 5.0 g of a binder PVDF, 390 g of a mixed solvent of water and ethanol (10 wt % ethanol), 2.5 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 2.5 g of a dispersant hydroxypropylmethylcellulose, and 0.1 g of a wetting agent glycerol were weighed and evenly stirred to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on both sides of a 7 μm polyethylene separator using extrusion coating method to obtain a coated polyethylene separator.
(4) The coated polyethylene separator was placed in a constant temperature oven to dry. The drying temperature was 60° C. and the drying time was 1 hour. The separator was marked as 7+2CP+2CP.
The morphology of the obtained modified composite polyethylene separator coating is shown in
(1) 8 g polyacrylonitrile was dissolved in 92 g N-methylpyrrolidone (NMP), and stirred to obtain a PAN solution with a mass concentration of 8% in the example. PAN nanofibers were prepared therefrom by electrospinning method.
(2) 5 g of PAN nanofibers (average diameter of the nanofibers: 400 nm, aspect ratio in the range of 10-300) and 95 g of magnesium oxide were weighed and dispersed in 240 g of water, and stirred at high speed to obtain a PAN nanofiber/magnesium oxide dispersion. Then 5.0 g of sodium carboxymethyl cellulose was weighed and dissolved in 150 g of water to fully dissolve it. The above two slurries were mixed and stirred evenly to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on both sides of a 12 μm polypropylene separator using microgravure coating method to obtain a coated polypropylene separator.
(4) The coated polypropylene separator was placed in a constant temperature oven to dry. The drying temperature was 60° C. and the drying time was 1 hour. The thickness of the dried coating was 3 μm and the separator was marked as 12+3CP+3CP.
The morphology of the obtained modified composite polypropylene separator coating is shown in
A Polyimide/Silica Nanofiber/Li7La3Zr2O12 (LLZO) Garnet Type Solid Oxide Electrolyte Coated Polyethylene Separator
(1) 90 g of the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighted in a molar ratio of 1:1, and added to the solvent N,N-dimethylformamide (DMF) to synthesize and obtain a polyamic acid solution with a mass concentration of 12% in the example. 10 g TEOS was added and stirred evenly. Polyamic acid nanofibers were prepared therefrom by electrospinning method. The nanofibers were placed in a high-temperature furnace for imidization treatment. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining at 300° C. for 1 hour to obtain polyimide/silica nanofibers, which contain silica on the surface and inside of the fibers.
(2) 1 g of polyimide/silica nanofibers (average diameter of the fibers: 350 nm, aspect ratio in the range of 15-450), 99 g of LLZO, 5 g of polyacrylamide, 1.8 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, and 0.5 g of a dispersant hydroxypropylmethylcellulose, 0.5 g of a wetting agent glycerol, and 0.2 g of a defoaming agent were solved in 140 g of water and sufficiently stirred to dissolve to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment. The slurry was then evenly coated on both sides of a 7 μm polyethylene separator using microgravure coating method.
(4) The coated polyethylene separator was placed in a constant temperature oven to dry. The drying temperature was 55° C. and the drying time was 0.5 hour.
The morphology of the obtained modified composite polyethylene separator is shown in
(1) the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, and reacted in the solvent N,N-dimethylformamide (DMF) to obtain a polyamic acid solution with a mass concentration of 10% in the example. PAA nanofibers were prepared therefrom by electrospinning method. The temperature of the obtained fibers was raised from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour to obtain polyimide nanofibers.
(2) 20 g of polyimide nanofibers (average diameter of the nanofibers: 270 nm, aspect ratio in the range of 10-280), 80 g of boehmite (average particle size of 500 nm), 1.5 g of sodium carboxymethylcellulose, 175 g of a mixed solvent of water and ethanol (ethanol 5 wt %), 0.3 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 0.3 g of a dispersant hydroxypropyl methylcellulose, 0.06 g of a wetting agent glycerol were weighed and stirred evenly to obtain a coating slurry.
(3) The stirred coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on both sides of a 7 μm polyethylene separator using microgravure coating method to obtain a coated modified separator.
(4) The coated modified separator was placed in a constant temperature oven to dry. The drying temperature was 55° C. and the drying time was 1 hour. The obtained modified composite polyethylene separator was marked as 7+2CP+2CP.
The preparation process of Examples 3.7-3.8 was the same as that of Example 2.6, except that the inorganic particles used in the coating were different.
(1) PVDF was dissolved in the solvent N,N-dimethylacetamide (DMAc) to obtain a PVDF solution with a mass concentration of 8% in the example. PVDF nanofibers were prepared therefrom with blowing electrospinning method.
Steps (2)-(4) were the same as those in Example 3.6.
(1) the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, and reacted in the solvent N,N-dimethylformamide (DMF) to obtain a polyamic acid solution with a mass concentration of 10% in the example. Nano barium titanate (mass ratio of PAA: barium titanate of 95:5) was added thereto, stirred thoroughly. PAA hybrid nanofibers were prepared therefrom by electrospinning method. The obtained nanofibers were subjected to imidization treatment in a high-temperature furnace. The temperature-raising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining at 300° C. for 1 hour to obtain polyimide/barium titanate hybrid nanofibers.
Steps (2)-(4) were the same as those in Example 3.6 except that the inorganic particles were changed to barium titanate.
(1) 7.5 g polyetherimide was solved in 92.5 g N-methylpyrrolidone (NMP), stirred to obtain a polyetherimide solution with a mass concentration of 8% in the example. Polyetherimide nanofibers were prepared therefrom by blowing spinning method.
Steps (2)-(4) were the same as those in Example 3.6.
(1) 7.5 g polyacrylonitrile was solved in 92.5 g N-methylpyrrolidone (NMP), stirred to obtain a PAN solution with a mass concentration of 7.5% in the example. Polyacrylonitrile nanofibers were prepared therefrom by blowing spinning method.
Steps (2)-(4) were the same as those in Example 3.6.
(1) 7.5 g P84 was solved in 92.5 g N-methylpyrrolidone (NMP), stirred to obtain a P84 solution with a mass concentration of 7.5% in the example. P84 nanofibers were prepared therefrom by blowing spinning method.
Steps (2)-(4) were the same as those in Example 3.6.
(1) 7.5 g PET was solved in 92.5 g xylenol, stirred to obtain a PET solution with a mass concentration of 7.5% in the example. PET nanofibers were prepared therefrom with blowing spinning method.
Steps (2)-(4) were the same as those in Example 3.6.
(1) 3.5 g of cellulose was dissolved in 96.5 g of xylenol, stirred to obtain a cellulose solution with a mass concentration of 3.5% in the example. Cellulose nanofibers were prepared therefrom with blowing spinning method.
Steps (2)-(4) were the same as those in Example 3.6.
The test results of test performance of Examples 3.6-3.15 are shown in Table 13.
(1) the monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, and reacted in the solvent N,N-dimethylformamide (DMF) to obtain a polyamic acid solution with a mass concentration of 10% in the example. PAA nanofibers were prepared therefrom by electrospinning method. The fibers were subjected to imidization treatment in a high temperature furnace. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour and obtaining polyimide nanofibers.
(2) 0.4 g of polyimide nanofibers, 99.6 g of boehmite (average particle size of 500 nm), 1.5 g of sodium carboxymethyl cellulose, 175 g of a mixed solvent of water and ethanol (ethanol 5 wt %), 0.3 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 0.3 g of a dispersant hydroxypropylmethylcellulose, 0.06 g of a wetting agent glycerol were weighed and thoroughly stirred to obtain a coating slurry.
(3) The coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on both sides of a 9 μm polyethylene separator using microgravure coating method to obtain a coated modified separator. The thickness of the coating after drying was 2 μm.
(4) The coated modified separator was placed in a constant temperature oven to dry. The drying temperature was 55° C. and the drying time was 1 hour. The obtained modified composite separator was marked as 9+2CP+2CP respectively. The thickness of the modified composite polyethylene separator is 13 μm.
The preparation process of Examples 3.17-3.24 and Comparative Example 1 (3.C1) and Comparative Example 2 (3.C2) were the same as those of Example 3.16, except that the amounts of polyimide nanofibers and boehmite were different. The specific compositions and test results are shown in Table 14.
(1) The monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, reacted in the solvent N,N-dimethylformamide (DMF) to obtain a polyamic acid solution with a mass concentration of 10% in the example. PAA nanofibers were prepared therefrom by electrospinning method. The fibers were subjected to imidization treatment in a high temperature furnace. The temperature rising program was: rising from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour to obtain polyimide nanofibers.
(2) The monomer pyromellitic dianhydride (PMDA) and the monomer 4,4′-diaminodiphenyl ether (ODA) were weighed at a molar ratio of 1:1, reacted in the solvent N,N-dimethylformamide (DMF) to obtain a clear and transparent polyamic acid solution with a mass concentration of 10%. PAA microspheres were prepared therefrom by electrostatic blowing method. The temperature of the obtained microspheres was raised from room temperature to 300° C. at a heating rate of 5° C./min, maintaining for 1 hour and obtaining polyimide microspheres.
(3) 35 g of polyimide microspheres (average particle size of the microspheres: 750 nm), 5.4 g of polyimide nanofibers, 59.6 g of silica (average particle size of 500 nm), 1.5 g of sodium carboxymethyl cellulose, 175 g of a mixed solvent of water and ethanol (ethanol 5 wt %), 0.3 g of a surfactant perfluoroalkyl ether quaternary ammonium salt, 0.3 g of a dispersant hydroxypropylmethylcellulose, 0.06 g of a wetting agent glycerol were weighed and evenly stirred to obtain a coating slurry.
(4) The coating slurry was put into a vacuum oven for 1 hour for defoaming treatment, and then evenly coated on both sides of a 7 μm polyethylene separator using microgravure coating method to obtain a coated modified separator. The thickness of the coating after drying was 2 μm.
(5) The coated modified separator was placed in a constant temperature oven to dry. The drying temperature was 55° C. and the drying time was 1 hour. The obtained modified composite polyethylene separator was marked as 7+2CP+2CP. The thickness of the modified composite polyethylene separator is 11 μm. The performance test results are shown in Table 15.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111229530.X | Oct 2021 | CN | national |
| 202111572973.9 | Dec 2021 | CN | national |
| 202210129640.7 | Feb 2022 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/126445 | 10/20/2022 | WO |
