CN110911638A - Lithium ion battery with high-voltage ternary material doped with lithium manganate and preparation method - Google Patents
Lithium ion battery with high-voltage ternary material doped with lithium manganate and preparation method Download PDFInfo
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Abstract
The invention discloses a high-voltage ternary material lithium manganate-doped lithium ion battery, which relates to the field of lithium batteries and comprises a positive plate, a negative plate, electrolyte and a fiber diaphragm, wherein the positive plate comprises an aluminum foil current collector and positive slurry, and the positive slurry comprises the following components in percentage by mass: 48-49% of ternary material, 48-49% of lithium manganate, 1.5-2.0% of conductive agent and 1.0-2.0% of polyvinylidene fluoride, wherein the negative plate comprises a copper foil current collector and negative slurry, and the negative slurry comprises the following components in percentage by mass: 96-98% of a negative active material, 1-2% of carboxymethyl cellulose and 1-2% of styrene butadiene rubber; the negative active material is artificial graphite. The invention also discloses a preparation method of the battery. The invention has the beneficial effects that the composite anode is prepared by adopting the lithium manganate and the ternary material, and the rate characteristic of the lithium ion battery is improved by improving the voltage range of the ternary doped lithium manganate system; and meanwhile, the production cost of the anode material is reduced.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-voltage ternary material lithium manganate-doped lithium ion battery and a preparation method thereof.
Background
With the development of electronic products such as smart phones and tablet computers, higher and higher requirements are put forward on the energy density of lithium ion batteries. Generally, two methods are available for improving the energy density of the battery, namely, the capacity of an electrode material is improved; and secondly, the working voltage of the battery is improved.
The energy density of lithium ion batteries depends to a large extent on the positive electrode material, and currently, LiCoO is the dominant positive electrode material for commercialization2、LiMn2O4、LiFePO4And ternary material LiMO2(NCM)。LiCoO2The production process is simple, the rate performance is excellent, but the price is expensive, and serious potential safety hazards exist. LiMn2O4The raw materials are cheap and have lower price, but the cycle performance is poorer. LiFePO4The discharge platform is moderate, the price is relatively cheap, the safety performance is excellent, but the specific energy of the material is relatively low. LiMO2The (NCM) uses manganese and nickel to replace part of cobalt in lithium cobaltate to obtain a ternary positive electrode material containing different transition metals, and the material has higher gram capacity (150-200 mAh/g), lower price than lithium cobaltate, but general safety performance.
In the prior art, a ternary doped lithium manganate system is generally applied to the fields of a 4.2V system of a soft package battery and a power battery. But has the problems of low gram capacity exertion of the battery and high production cost.
Therefore, it is highly desirable to develop a lithium ion battery doped with lithium manganate as a ternary material, and to improve the rate capability of the lithium ion battery and reduce the production cost by doping the lithium manganate with a high-voltage ternary material.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: a lithium ion battery with high-voltage ternary material doped with lithium manganate is provided.
The technical solution of the invention is as follows:
the utility model provides a lithium ion battery of high voltage ternary material doping lithium manganate, includes positive plate, negative pole piece, electrolyte, fibre diaphragm, the positive plate includes aluminium foil mass flow body and anodal thick liquids, each component mass ratio is in anodal thick liquids: 48-49% of ternary material, 48-49% of lithium manganate, 1.5-2.0% of conductive agent and 1.0-2.0% of polyvinylidene fluoride, wherein the negative plate comprises a copper foil current collector and negative electrode slurry, and the negative electrode slurry comprises the following components in percentage by mass: 96-98% of a negative active material, 1-2% of carboxymethyl cellulose and 1-2% of styrene butadiene rubber, wherein the negative active material is artificial graphite.
Further, the electrolyte is high-voltage-resistant electrolyte and comprises solute, solvent and additive, wherein the solute is LiPF6The solvent is ethylene carbonate or methyl ethyl carbonate, and the additive is tris (trimethylsilane) borate, methylene methanedisulfonate, succinonitrile or diethyl carbonate; the mass ratio of the ethylene carbonate to the methyl ethyl carbonate is 6: 10; the tris (trimethylsilane) borate, the methylene methanedisulfonate, the succinonitrile and the diethyl carbonate respectively account for 1 percent, 0.5 percent, 1.5 percent and 0.8 percent of the mass of the electrolyte; the LiPF6Accounting for 12 percent of the mass fraction of the electrolyte.
Further, the fiber membrane is a polyimide fiber membrane synthesized by an electrostatic spinning method, the air permeability of the fiber membrane is 70-250 sec/100ml, and the thickness of the fiber membrane is 7-15 mm.
Further, the ternary material is a single crystal ternary material; the lithium manganate is a single-crystal lithium manganate material; the positive conductive agent is carbon nano tube and conductive carbon black; the mass ratio of the carbon nano tube to the conductive carbon black is 1: 0.5-1.5.
Further, the negative active material is artificial graphite compounded by primary particles and secondary particles, and the mass ratio of the primary particles to the secondary particles is 1-5: 5-9.
Further, the working voltage of the high-voltage ternary material doped lithium manganate lithium ion battery is 3-4.35V.
A preparation method of a high-voltage ternary material lithium manganate doped lithium ion battery comprises the following steps:
(1) manufacturing a positive plate: adding a ternary material, lithium manganate, a carbon nano tube, conductive carbon black and polyvinylidene fluoride into N-methyl pyrrolidone to prepare anode slurry, then coating the anode slurry on an aluminum foil, and sequentially drying, rolling, slitting and tabletting to prepare an anode sheet containing 1 tab;
(2) and (3) manufacturing a negative plate: adding artificial graphite, carboxymethyl cellulose and styrene butadiene rubber into water to prepare negative electrode slurry, then coating the negative electrode slurry on copper foil, and sequentially drying, rolling, slitting and manufacturing to obtain a negative electrode sheet containing 1 tab;
(3) assembling the battery: matching the positive plate and the negative plate prepared in the step (1) and the step (2) with a polyimide fiber diaphragm, winding, and finally injecting electrolyte to assemble a soft package battery;
(4) pre-charging and grading of the battery: the battery pre-charging capacity is 85%, and the aging time is 1-6 d at 45 ℃; the capacity grading discharge cut-off voltage of the battery is 3.0V, and the charge cut-off voltage is 4.35V.
Further, the preparation method of the fiber membrane in the step (3) comprises the following steps:
s1, respectively weighing the components in a molar ratio of 1: 1.01 dissolving 4, 4-diaminodiphenyl ether and pyromellitic dianhydride in tetrahydrofuran-methanol mixed solvent in the mass ratio of 4:1 in an ice-water bath, stirring to dissolve completely, keeping the ice-water bath, adding pyromellitic dianhydride into the reaction system in several times, gradually changing the solution from clear to milky turbid, and continuously stirring until uniform milky viscous substances are formed, thus obtaining the polyamide acid solution;
s2, adding tetraethoxysilane into the polyamic acid solution in the step S1 for multiple times, wherein the adding amount of each time is 1-3 ml, the interval time of the two times is 8-12 min, and the total adding amount of tetraethoxysilane is the theoretical calculation value of tetraethoxysilane required by the fact that the mass of silicon dioxide generated by the hydrolysis of the tetraethoxysilane accounts for 20% of the mass of polyimide generated by the complete imidization of the polyamic acid solution; finally, fully stirring for 150min to obtain a mixed solution;
s3, placing the mixed solution in the step S2 as a spinning solution into an injection pump of a high-voltage electrostatic spinning machine, connecting a needle head of the injection pump with a high-voltage generating device, and maintaining the spinning state on the high-voltage electrostatic spinning machine for more than 12 hours to obtain a fiber diaphragm; and (3) placing the obtained fiber diaphragm in a high-temperature blast drying oven, carrying out pressure reduction treatment, and carrying out temperature programming to 85 ℃ for 12 hours to obtain the polyimide fiber diaphragm.
Further, the preparation method of the electrolyte in the step (3) comprises the following steps: in a glove box filled with argon, ethylene carbonate and methyl ethyl carbonate are uniformly mixed, tris (trimethylsilane) borate, methyl methylene methanedisulfonate, succinonitrile and diethyl carbonate are added into the mixed solution, and LiPF is slowly added6And stirring until the electrolyte is completely dissolved to obtain the high-voltage-resistant electrolyte.
Further, in the step (1), the double-sided coating density of the positive plate is 0.32g/1540.25mm2The compacted density of the positive plate is 3.1g/cm3(ii) a In the step (2), the double-sided coating density of the negative plate is 0.135g/1540.25mm2The compacted density of the negative pole piece is 1.6g/cm3。
The invention has the beneficial effects that:
1. according to the invention, the composite positive electrode is prepared from the lithium manganate and the ternary material, so that the voltage range of a ternary doped lithium manganate system is increased, and compared with the working voltage range of 3-4.2V of the battery in the prior art, the working voltage of the battery is 3-4.35V; the operating voltage is improved, and the rate characteristic of the lithium ion battery is improved. In addition, the ternary material is cheaper, so that the production cost is reduced, and the problems of low gram capacity exertion and high production cost of the battery in the prior art are solved.
2. Compared with the polyolefin diaphragm, the fiber diaphragm provided by the invention has better mechanical strength, and the difference between the liquid absorption rate, the porosity, the expansion and contraction rate and the thermal property of the fiber diaphragm is not great, so that the safety performance of the battery is improved.
3. Compared with the electrolyte in the prior art, the electrolyte has the characteristic of high pressure resistance.
4. Tests show that the lithium battery prepared by the invention has 0.5C/0.5C cycle for 500 weeks, and the capacity retention rate is more than 80 percent; the 2C multiplying power is more than 70 percent; the film is stored for 4 hours at 85 ℃, the thickness change rate is less than 10 percent, and the capacity retention rate is more than 85 percent.
5. On one hand, the composite positive electrode is prepared from the lithium manganate and the ternary material, so that the voltage range of the lithium battery is enlarged, and the rate characteristic of the lithium battery is improved; on the other hand, the working voltage of the battery is 3-4.35V, which is higher than that of the battery in the prior art, so that the electrolyte and the diaphragm in the prior art are not suitable for the battery in the invention, and on the other hand, the electrolyte and the diaphragm in the invention have the characteristic of high pressure resistance by improving the electrolyte and the diaphragm, so that the battery is not only suitable for the lithium battery in the invention, but also improves the safety performance of the battery in the invention.
Drawings
FIG. 1 is a magnification chart of example 1 of the present invention and a comparative example.
Detailed Description
Example 1
(1) Manufacturing a positive plate: adding 48kg of single crystal ternary material, 48.5kg of single crystal lithium manganate material, 1kg of carbon nano tube, 0.5kg of conductive carbon black and 2kg of polyvinylidene fluoride into N-methyl pyrrolidone (NMP) to prepare anode slurry, then coating the anode slurry on an aluminum foil, and sequentially drying, rolling, slitting and tabletting to obtain an anode sheet containing 1 tab; wherein, when the coating is controlled, the double-sided coating density of the positive plate pole piece is 0.32g/1540.25mm2The compaction density of the positive plate is 3.1g/cm during rolling3。
(2) And (3) manufacturing a negative plate: adding 96kg of artificial graphite, 1kg of carboxymethyl cellulose and 3kg of styrene butadiene rubber into water to prepare negative electrode slurry, then coating the negative electrode slurry on copper foil, and sequentially drying, rolling, slitting and manufacturing the negative electrode sheet containing 1 tab; wherein, when coating is controlled, the double-sided coating density of the negative plate is 0.135g/1540.25mm2The compaction density of the negative plate is 1.6g/cm during rolling3。
(3) Manufacturing a fiber diaphragm:
s1, respectively weighing 2g of 4, 4-diaminodiphenyl ether and 2.03g of pyromellitic dianhydride, dissolving the 4, 4-diaminodiphenyl ether in 45 ml of tetrahydrofuran-methanol mixed solvent in an ice water bath, wherein the mass ratio of tetrahydrofuran to methanol is 4:1, stirring to completely dissolve, keeping the ice water bath, adding the pyromellitic dianhydride into the reaction system in several times, gradually changing the solution from clear to milky turbid, and continuously stirring until a uniform milky viscous substance is formed, thus obtaining a polyamide acid solution;
s2, adding 1-3 ml of tetraethoxysilane into the polyamic acid solution in the step S1 in five times, wherein the interval time between the two times is 8-12 min, and the total adding amount of tetraethoxysilane is 15.8 g; finally, fully stirring for 150min to obtain a mixed solution;
s3, placing the mixed solution in the step S2 as a spinning solution into an injection pump of a high-voltage electrostatic spinning machine, connecting a needle head of the injection pump with a high-voltage generating device, and maintaining the spinning state on the high-voltage electrostatic spinning machine for more than 12 hours to obtain a fiber diaphragm; and (3) placing the obtained fiber diaphragm in a high-temperature blast drying oven, carrying out pressure reduction treatment, and carrying out temperature programming to 85 ℃ for 12 hours to obtain the polyimide fiber diaphragm.
(4) Preparing electrolyte: 31.95kg of ethylene carbonate and 53.25kg of methyl ethyl carbonate are uniformly mixed in a glove box filled with argon, 1kg of tris (trimethylsilane) borate, 0.5kg of methylene methanedisulfonate, 1.5kg of succinonitrile and 0.8kg of diethyl carbonate are added into the mixed solution, 12kg of LiPF6 is slowly added, and the mixture is stirred until the mixture is completely dissolved, so that the high-voltage resistant electrolyte is obtained.
(5) Assembling the battery: matching the positive plate and the negative plate prepared in the steps (1) and (2) with the polyimide fiber diaphragm prepared in the step (3), winding, and finally injecting the electrolyte in the step (4) to assemble a soft package battery;
(6) pre-charging and grading of the battery: the battery pre-charging capacity is 85%, and the aging time is 1-6 d at 45 ℃; the capacity grading discharge cut-off voltage of the battery is 3.0V, and the charge cut-off voltage is 4.35V.
Through tests, the soft package battery prepared in the embodiment has a capacity retention rate of 83% after 0.5C/0.5C cycle for 500 weeks; the 2C multiplying power is 75 percent; the film is stored for 4 hours at 85 ℃, the thickness change rate is 6 percent, and the capacity retention rate is 87 percent.
Example 2
(1) Manufacturing a positive plate: adding 48.5kg of single crystal ternary material, 48.5kg of single crystal lithium manganate material, 1kg of carbon nano tube, 1kg of conductive carbon black and 1kg of polyvinylidene fluoride into N-methyl pyrrolidone (NMP) to prepare anode slurry, then coating the anode slurry on an aluminum foil, and sequentially drying, rolling, slitting and tabletting to obtain an anode sheet containing 1 tab; wherein, when the coating is controlled, the double-sided coating density of the positive plate pole piece is 0.32g/1540.25mm2The compaction density of the positive plate is 3.1g/cm during rolling3。
(2) And (3) manufacturing a negative plate: adding 97kg of artificial graphite, 1kg of carboxymethyl cellulose and 2kg of styrene butadiene rubber into water to prepare negative electrode slurry, then coating the negative electrode slurry on copper foil, and sequentially drying, rolling, slitting and manufacturing to obtain a negative electrode sheet containing 1 tab; wherein, when coating is controlled, the double-sided coating density of the negative plate is 0.135g/1540.25mm2The compaction density of the negative plate is 1.6g/cm during rolling3。
Steps (3), (4), (5) and (6) are the same as those in example 1.
Through tests, the soft package battery prepared by the embodiment has 0.5C/0.5C cycle for 500 weeks, and the capacity retention rate is 85%; the 2C multiplying power is 78%; the film was stored at 85 ℃ for 4 hours, the thickness change rate was 8%, and the capacity retention rate was 89%.
Example 3
(1) Manufacturing a positive plate: adding 49kg of single crystal ternary material, 48kg of single crystal lithium manganate material, 1kg of carbon nano tube, 0.5kg of conductive carbon black and 1.5kg of polyvinylidene fluoride into N-methyl pyrrolidone (NMP) to prepare anode slurry, then coating the anode slurry on aluminum foil, and sequentially drying, rolling, slitting and tabletting to obtain an anode sheet containing 1 tab; wherein, when the coating is controlled, the double-sided coating density of the positive plate pole piece is 0.32g/1540.25mm2The compaction density of the positive plate is 3.1g/cm during rolling3。
(2) And (3) manufacturing a negative plate: adding 97kg of artificial graphite, 1.5kg of carboxymethyl cellulose and 1.5kg of styrene butadiene rubber into water to prepare negative electrode slurry, then coating the negative electrode slurry on copper foil, and sequentially drying, rolling, slitting and making a negative electrode sheet containing 1 tab; wherein, when coating is controlled, the double-sided coating density of the negative plate is 0.135g/1540.25mm2The compaction density of the negative plate is 1.6g/cm during rolling3。
Steps (3), (4), (5) and (6) are the same as those in example 1.
Through tests, the soft package battery prepared in the embodiment has 0.5C/0.5C cycle for 500 weeks, and the capacity retention rate is 89%; the 2C multiplying power is 80%; the film was stored at 85 ℃ for 4 hours, the thickness change rate was 7%, and the capacity retention rate was 88%.
Example 4
(1) Manufacturing a positive plate: adding 49kg of single crystal ternary material, 48kg of single crystal lithium manganate material, 0.5kg of carbon nano tube, 0.5kg of conductive carbon black and 2kg of polyvinylidene fluoride into N-methyl pyrrolidone (NMP) to prepare anode slurry, then coating the anode slurry on aluminum foil, and sequentially drying, rolling, slitting and tabletting to obtain an anode sheet containing 1 tab; wherein, when the coating is controlled, the double-sided coating density of the positive plate pole piece is 0.32g/1540.25mm2The compaction density of the positive plate is 3.1g/cm during rolling3。
(2) And (3) manufacturing a negative plate: adding 98kg of artificial graphite, 1.5kg of carboxymethyl cellulose and 0.5kg of styrene-butadiene rubber into water to prepare negative electrode slurryThen coating the negative electrode slurry on copper foil, and sequentially drying, rolling, slitting and manufacturing the copper foil to obtain a negative electrode sheet containing 1 tab; wherein, when coating is controlled, the double-sided coating density of the negative plate is 0.135g/1540.25mm2The compaction density of the negative plate is 1.6g/cm during rolling3。
Steps (3), (4), (5) and (6) are the same as those in example 1.
Through tests, the soft package battery prepared in the embodiment has a capacity retention rate of 84% after 0.5C/0.5C cycle for 500 weeks; the 2C multiplying power is 74 percent; the film was stored at 85 ℃ for 4 hours, the thickness change rate was 8%, and the capacity retention rate was 86%.
Comparative example
(1) Manufacturing a positive plate: 96.5kg of single crystal ternary material, 1kg of carbon nanotubes, 0.5kg of conductive carbon black and 2kg of polyvinylidene fluoride were added to N-methylpyrrolidone (NMP) to prepare positive electrode slurry. The rest is the same as example 1.
The results of the rate tests of the batteries prepared in the embodiment 1 and the comparative example are shown in fig. 1, and it can be seen from fig. 1 that the rate characteristics of the battery are improved in the embodiment 1 compared with the ternary battery in the comparative example, so that the invention can be seen that the voltage range of the lithium battery of the invention is improved and the rate characteristics of the lithium ion battery are improved by compounding the lithium manganate and the ternary material to prepare the composite anode of the invention and matching the high-voltage resistant electrolyte and the fiber diaphragm.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (10)
1. A lithium ion battery of high-voltage ternary material doped lithium manganate is characterized in that: the anode plate comprises an aluminum foil current collector and anode slurry, wherein the anode plate comprises an anode plate, a cathode plate, electrolyte and a fiber diaphragm, and the anode slurry comprises the following components in percentage by mass: 48-49% of ternary material, 48-49% of lithium manganate, 1.5-2.0% of conductive agent and 1.0-2.0% of polyvinylidene fluoride, wherein the negative plate comprises a copper foil current collector and negative electrode slurry, and the negative electrode slurry comprises the following components in percentage by mass: 96-98% of a negative active material, 1-2% of carboxymethyl cellulose and 1-2% of styrene butadiene rubber, wherein the negative active material is artificial graphite.
2. The lithium ion battery of claim 1, wherein the high-voltage ternary material is doped with lithium manganate, and the lithium ion battery is characterized in that: the electrolyte is high-voltage-resistant electrolyte and comprises solute, solvent and additive, wherein the solute is LiPF6The solvent is ethylene carbonate or methyl ethyl carbonate, and the additive is tris (trimethylsilane) borate, methylene methanedisulfonate, succinonitrile or diethyl carbonate; the mass ratio of the ethylene carbonate to the methyl ethyl carbonate is 6: 10; the tris (trimethylsilane) borate, the methylene methanedisulfonate, the succinonitrile and the diethyl carbonate respectively account for 1 percent, 0.5 percent, 1.5 percent and 0.8 percent of the mass of the electrolyte; the LiPF6Accounting for 12 percent of the mass fraction of the electrolyte.
3. The lithium ion battery of claim 1, wherein the high-voltage ternary material is doped with lithium manganate, and the lithium ion battery is characterized in that: the fiber membrane is a polyimide fiber membrane synthesized by an electrostatic spinning method, the air permeability of the fiber membrane is 70-250 sec/100ml, and the thickness of the fiber membrane is 7-15 mm.
4. The lithium ion battery of claim 1, wherein the high-voltage ternary material is doped with lithium manganate, and the lithium ion battery is characterized in that: the ternary material is a single crystal ternary material; the lithium manganate is a single-crystal lithium manganate material; the positive conductive agent is carbon nano tube and conductive carbon black; the mass ratio of the carbon nano tube to the conductive carbon black is 1: 0.5-1.5.
5. The lithium ion battery of claim 1, wherein the high-voltage ternary material is doped with lithium manganate, and the lithium ion battery is characterized in that: the negative electrode active material is artificial graphite compounded by primary particles and secondary particles, and the mass ratio of the primary particles to the secondary particles is 1-5: 5-9.
6. The lithium ion battery of claim 1, wherein the high-voltage ternary material is doped with lithium manganate, and the lithium ion battery is characterized in that: the working voltage of the high-voltage ternary material doped lithium manganate lithium ion battery is 3-4.35V.
7. The preparation method of the lithium ion battery doped with the high-voltage ternary material lithium manganate according to any one of claims 1 to 6, characterized by comprising the following steps: the method comprises the following steps:
(1) manufacturing a positive plate: adding a ternary material, lithium manganate, a carbon nano tube, conductive carbon black and polyvinylidene fluoride into N-methyl pyrrolidone to prepare anode slurry, then coating the anode slurry on an aluminum foil, and sequentially drying, rolling, slitting and tabletting to prepare an anode sheet containing 1 tab;
(2) and (3) manufacturing a negative plate: adding artificial graphite, carboxymethyl cellulose and styrene butadiene rubber into water to prepare negative electrode slurry, then coating the negative electrode slurry on copper foil, and sequentially drying, rolling, slitting and manufacturing to obtain a negative electrode sheet containing 1 tab;
(3) assembling the battery: matching the positive plate and the negative plate prepared in the step (1) and the step (2) with a polyimide fiber diaphragm, winding, and finally injecting electrolyte to assemble a soft package battery;
(4) pre-charging and grading of the battery: the battery pre-charging capacity is 85%, and the aging time is 1-6 d at 45 ℃; the capacity grading discharge cut-off voltage of the battery is 3.0V, and the charge cut-off voltage is 4.35V.
8. The preparation method of the lithium ion battery doped with the high-voltage ternary material lithium manganate according to claim 7, characterized by comprising the following steps: the preparation method of the fiber membrane in the step (3) comprises the following steps:
s1, respectively weighing the components in a molar ratio of 1: 1.01 dissolving 4, 4-diaminodiphenyl ether and pyromellitic dianhydride in tetrahydrofuran-methanol mixed solvent in the mass ratio of 4:1 in an ice-water bath, stirring to dissolve completely, keeping the ice-water bath, adding pyromellitic dianhydride into the reaction system in several times, gradually changing the solution from clear to milky turbid, and continuously stirring until uniform milky viscous substances are formed, thus obtaining the polyamide acid solution;
s2, adding tetraethoxysilane into the polyamic acid solution in the step S1 for multiple times, wherein the adding amount of each time is 1-3 ml, the interval time of the two times is 8-12 min, and the total adding amount of tetraethoxysilane is the theoretical calculation value of tetraethoxysilane required by the fact that the mass of silicon dioxide generated by the hydrolysis of the tetraethoxysilane accounts for 20% of the mass of polyimide generated by the complete imidization of the polyamic acid solution; finally, fully stirring for 150min to obtain a mixed solution;
s3, placing the mixed solution in the step S2 as a spinning solution into an injection pump of a high-voltage electrostatic spinning machine, connecting a needle head of the injection pump with a high-voltage generating device, and maintaining the spinning state on the high-voltage electrostatic spinning machine for more than 12 hours to obtain a fiber diaphragm; and (3) placing the obtained fiber diaphragm in a high-temperature blast drying oven, carrying out pressure reduction treatment, and carrying out temperature programming to 85 ℃ for 12 hours to obtain the polyimide fiber diaphragm.
9. The preparation method of the lithium ion battery doped with the high-voltage ternary material lithium manganate according to claim 7, characterized by comprising the following steps: the preparation method of the electrolyte in the step (3) comprises the following steps: in a glove box filled with argon, ethylene carbonate and methyl ethyl carbonate are uniformly mixed, tris (trimethylsilane) borate, methyl methylene methanedisulfonate, succinonitrile and diethyl carbonate are added into the mixed solution, and LiPF is slowly added6And stirring until the electrolyte is completely dissolved to obtain the high-voltage-resistant electrolyte.
10. The preparation method of the lithium ion battery doped with the high-voltage ternary material lithium manganate according to claim 7, characterized by comprising the following steps: in the step (1), the double-sided coating density of the positive plate is 0.32g/1540.25mm2The compacted density of the positive plate is 3.1g/cm3(ii) a In the step (2), the double-sided coating density of the negative plate is 0.135g/1540.25mm2The compacted density of the negative pole piece is 1.6g/cm3。
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