In-situ forming polymer composite electrolyte-positive electrode integrated material, preparation method thereof and lithium metal battery
阅读说明：本技术 一种原位成型聚合物复合电解质-正极一体化材料、其制备方法及锂金属电池 (In-situ forming polymer composite electrolyte-positive electrode integrated material, preparation method thereof and lithium metal battery ) 是由 姚霞银 徐芳林 于 2019-10-09 设计创作，主要内容包括：本发明提供了一种原位成型聚合物复合电解质-正极一体化材料、其制备方法及锂金属电池。本发明提供的原位成型聚合物复合电解质-正极一体化材料的制备方法,在形成电解质时无需使用溶剂,避免溶剂对电池性能的影响；且采用特定的原料在正极片上进行原位成型,能够与电池正极形成三维接触,减小电荷传递阻抗,提高电池的电化学性能。(The invention provides an in-situ forming polymer composite electrolyte-anode integrated material, a preparation method thereof and a lithium metal battery. According to the preparation method of the in-situ forming polymer composite electrolyte-anode integrated material, a solvent is not needed when the electrolyte is formed, so that the influence of the solvent on the performance of a battery is avoided; and the specific raw materials are adopted to carry out in-situ forming on the positive plate, so that three-dimensional contact can be formed with the positive electrode of the battery, the charge transfer impedance is reduced, and the electrochemical performance of the battery is improved.)
1. A preparation method of an in-situ forming polymer composite electrolyte-anode integrated material is characterized by comprising the following steps:
a) mixing a polymer monomer, a ceramic electrolyte and a lithium salt to obtain electrolyte slurry;
b) coating the electrolyte slurry on a positive plate, and carrying out in-situ curing molding to obtain an integrated material;
the polymer monomer has a polyether main chain and a reactive functional group;
the reaction functional group is one or more of carbon-carbon double bond, amido, sulfydryl, epoxy group, hydroxyl, isocyanate group and carboxyl.
2. The preparation method according to claim 1, wherein the polymer monomer is selected from one or more monomers shown in formula 1-formula 8;
3. the method according to claim 1, wherein the ceramic electrolyte is selected from one or more of the group consisting of electrolytes represented by formulas I to VI:
Li3+5xP1-xS4formula I; in the formula I, x is more than or equal to 0 and less than 1;
Li4-xGe1-xPxS4formula II; in the formula II, x is more than 0 and less than 1;
Li10+xG1+xP2-xS12formula III; in the formula III, x is 1 or 2, and G is Si, Ge or Sn;
Li1+xMxTi2-x(PO4)3a formula IV; in the formula IV, x is more than 0 and less than 2, and M is Al, In, Ge, Ga, Y, Lu or La;
Li0.5-3xLa0.5+xTiO3formula V; in the formula V, x is more than 0 and less than 0.15;
Li7-xLa3Zr2-xMxO12formula VI; in the formula VI, x is more than or equal to 0 and less than or equal to 2, and M is Zr, Hf, Sn, Nb, Y, W or Ta.
4. The method of claim 1, wherein the lithium salt is selected from LiN (CF)3SO2)2、LiN(FSO2)2、LiClO4、LiCF3SO3、LiBF4、LiPF4、LiAsF6And LiB (C)2O4)2One or more of them.
5. The production method according to claim 1 or 3, wherein the average particle diameter of the ceramic-type electrolyte is 5 to 500 nm.
6. The preparation method according to claim 1, wherein in the step a), the dosage of each raw material is as follows:
0.1-60 parts of a polymer monomer;
1-99.9 parts of ceramic electrolyte;
1-99.9 parts of lithium salt.
7. The preparation method according to claim 1, wherein in the step b), the positive electrode material of the positive electrode sheet is selected from one or more of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel cobalt oxide, lithium nickel phosphate and lithium cobalt phosphate.
8. The preparation method according to claim 1, wherein in the step b), the curing molding is thermal curing molding or ultraviolet curing molding;
in step a) an initiator and/or a catalyst is also added.
9. An in-situ forming polymer composite electrolyte-positive electrode integrated material prepared by the preparation method of any one of claims 1 to 8.
10. A lithium metal battery comprising the in-situ formed polymer composite electrolyte-cathode integrated material according to claim 9 and a cathode.
Technical Field
The invention relates to the field of lithium ion batteries, in particular to an in-situ forming polymer composite electrolyte-anode integrated material, a preparation method thereof and a lithium metal battery.
Background
Lithium ion batteries have been widely used in the production and life of people as one of the main energy storage modes at present. Commercial lithium ion batteries mainly use organic liquids as electrolytes, and have the following 2 problems: 1. the leakage is easy, the flammability is high, and certain potential safety hazard can be caused; 2. the lithium ion battery has the advantages that the lithium ion battery is not stable enough, lithium dendrite is easy to form in the circulation process, the application of the lithium metal as a negative electrode is limited, and the comprehensive performance of the lithium ion battery is difficult to be substantially and obviously improved.
In view of this, solid electrolytes, which can be mainly classified into ceramic structure type electrolytes, polymer electrolytes, and composite electrolyte materials combining the two, have been proposed instead of organic liquid electrolytes. The ceramic/polymer composite electrolyte material integrates the advantages of ceramic structure type electrolyte and polymer electrolyte, and has high ionic conductivity, good mechanical flexibility and strength.
The traditional ceramic/polymer composite electrolyte material is prepared as follows: mixing the ceramic structure type electrolyte particles with the polymer electrolyte in a corresponding solvent, and then coating and drying. It requires a large amount of solvent in the preparation process, and is difficult to completely dry and remove, which may affect the battery performance. On the other hand, the conventional ceramic/polymer composite electrolyte material has the problem that the unremoved solvent affects the battery performance if the conventional ceramic/polymer composite electrolyte material is directly coated on an electrode due to the existence of the solvent; for the battery assembled by the formed ceramic/polymer composite electrolyte material and the anode, because of the existence of the ceramic electrolyte particles, the contact between the ceramic/polymer composite electrolyte material and the anode is mainly point contact, the wettability is poor and the contact area is small, so that high charge transfer impedance is caused, and the comprehensive performance of the battery is influenced.
Disclosure of Invention
In view of the above, the present invention provides an in-situ forming polymer composite electrolyte-positive electrode integrated material, a preparation method thereof, and a lithium metal battery. According to the preparation method of the in-situ forming polymer composite electrolyte-positive electrode integrated material, a solvent is not needed when an electrolyte is formed, the influence of the solvent on the performance of a battery is avoided, and the specific raw materials are adopted for carrying out in-situ forming on the positive electrode plate, so that the three-dimensional contact with the positive electrode of the battery can be formed, the charge transfer impedance is reduced, and the electrochemical performance of the battery is improved.
The invention provides a preparation method of an in-situ forming polymer composite electrolyte-anode integrated material, which comprises the following steps:
a) mixing a polymer monomer, a ceramic electrolyte and a lithium salt to obtain electrolyte slurry;
b) coating the electrolyte slurry on a positive plate, and carrying out in-situ curing molding to obtain an integrated material;
the polymer monomer has a polyether main chain and a reactive functional group;
the reaction functional group is one or more of carbon-carbon double bond, amido, sulfydryl, epoxy group, hydroxyl, isocyanate group and carboxyl.
Preferably, the polymer monomer is selected from one or more monomers shown in formula 1-formula 8;
preferably, the ceramic electrolyte is selected from one or more of the electrolytes shown in formulas I to VI:
Li3+5xP1-xS4formula I; in the formula I, x is more than or equal to 0 and less than 1;
Li4-xGe1-xPxS4formula II; in the formula II, x is more than 0 and less than 1;
Li10+xG1+xP2-xS12formula III; in formula III, x is 1 or 2, and G is Si, Ge or Sn;
Li1+xMxTi2-x(PO4)3formula IV; in the formula IV, x is more than 0 and less than 2, and M is Al, In, Ge, Ga, Y, Lu or La;
Li0.5-3xLa0.5+xTiO3formula V; in the formula V, x is more than 0 and less than 0.15;
Li7-xLa3Zr2-xMxO12formula VI; in the formula VI, x is more than or equal to 0 and less than or equal to 2, and M is Zr, Hf, Sn, Nb, Y, W or Ta.
Preferably, the lithium salt is selected from LiN (CF)3SO2)2、LiN(FSO2)2、LiClO4、LiCF3SO3、LiBF4、LiPF4、LiAsF6And LiB (C)2O4)2One or more of them.
Preferably, the average particle size of the ceramic electrolyte is 5 to 500 nm.
Preferably, in the step a), the dosage of each raw material is as follows:
0.1-60 parts of a polymer monomer;
1-99.9 parts of ceramic electrolyte;
1-99.9 parts of lithium salt.
Preferably, in the step b), the positive electrode material of the positive electrode sheet is selected from one or more of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel cobalt oxide, lithium nickel phosphate and lithium cobalt phosphate.
Preferably, in the step b), the curing molding is thermosetting molding or ultraviolet curing molding;
in step a) an initiator and/or a catalyst is also added.
The invention also provides an in-situ forming polymer composite electrolyte-anode integrated material prepared by the preparation method in the technical scheme.
The invention also provides a lithium metal battery which comprises the in-situ forming polymer composite electrolyte-anode integrated material and the cathode in the technical scheme.
The invention provides a preparation method of an in-situ forming polymer composite electrolyte-anode integrated material, which comprises the following steps: a) mixing a polymer monomer, a ceramic electrolyte and a lithium salt to obtain electrolyte slurry; b) coating the electrolyte slurry on a positive plate, and carrying out in-situ curing molding to obtain an integrated material; the polymer monomer has a polyether main chain and a reactive functional group; the reaction functional group is one or more of carbon-carbon double bond, amido, sulfydryl, epoxy group, hydroxyl, isocyanate group and carboxyl.
In the invention, under the condition of no solvent, a specific polymer monomer is mixed with a ceramic electrolyte and a lithium salt to obtain electrolyte slurry; and then directly carrying out in-situ curing molding on the electrolyte slurry on the positive plate to obtain the electrolyte-positive plate integrated material. Firstly, in the process of forming the electrolyte slurry, a specific polymer monomer is adopted, so that the electrolyte slurry is obtained under the condition of no solvent, the solvent removing procedure is omitted, the problem that the solvent is difficult to remove is solved, and the influence of the solvent on the electrolyte and the battery performance is avoided; meanwhile, the solvent-free slurry is directly coated on the positive plate and can enter pores of the positive plate to form three-dimensional contact with the positive material, so that the charge transfer impedance is reduced; in addition, in the monomer in-situ curing and forming process, small molecules of the monomer are polymerized into a novel polymer which is cooperated with the ceramic electrolyte, so that the whole electrolyte material has high ionic conductivity.
The test result shows that the charge transfer impedance of the electrolyte/electrode is 175 omega-m2The electrochemical window of the battery reaches 0-6V, and the capacity retention rate after 500 cycles reaches more than 70%; the lithium ion conductivity of the electrolyte material is 1.5 multiplied by 10-5And more than S/cm.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic structural diagram of an electrolyte-cathode integrated material formed by in-situ curing according to the present invention.
Detailed Description
The invention provides a preparation method of an in-situ forming polymer composite electrolyte-anode integrated material, which comprises the following steps:
a) mixing a polymer monomer, a ceramic electrolyte and a lithium salt to obtain electrolyte slurry;
b) coating the electrolyte slurry on a positive plate, and carrying out in-situ curing molding to obtain an integrated material;
the polymer monomer has a polyether main chain and a reactive functional group;
the reaction functional group is one or more of carbon-carbon double bond, amido, sulfydryl, epoxy group, hydroxyl, isocyanate group and carboxyl.
According to the invention, a polymer monomer, a ceramic electrolyte and a lithium salt are mixed to obtain an electrolyte slurry.
In the invention, the polymer monomer has a polyether main chain and a reaction functional group; the reaction functional group is one or more of carbon-carbon double bond, amido, sulfydryl, epoxy group, hydroxyl, isocyanate group and carboxyl.
In the invention, preferably, the polymer monomer is selected from one or more monomers shown in formula 1-formula 8;
in the invention, the number average molecular weight Mn of the polymer monomer is preferably 500-1500. In some embodiments of the invention, the number average molecular weight Mn of the polymer is 500, 600, 1000, 1200 or 1500. The source of the polymer monomer is not particularly limited in the present invention, and may be generally commercially available or prepared according to a preparation method well known to those skilled in the art.
In one embodiment of the present invention, a monomer represented by formula 1 having a number average molecular weight of 1000 is used. In another embodiment of the present invention, the monomer represented by formula 2 having a number average molecular weight of 1500 is used. In another embodiment of the present invention, the monomer represented by formula 2 having a number average molecular weight of 1500 and the monomer represented by formula 3 having a number average molecular weight of 1000 are used. In another embodiment of the present invention, a monomer represented by formula 4 having a number average molecular weight of 1200 is used. In another embodiment of the present invention, the monomer represented by formula 2 having a number average molecular weight of 1500 and the monomer represented by formula 5 having a number average molecular weight of 500 are used. In another embodiment of the present invention, the monomer represented by formula 2 having a number average molecular weight of 1500 and the monomer represented by formula 6 having a number average molecular weight of 1000 are used. In another embodiment of the present invention, the monomer represented by formula 2 having a number average molecular weight of 1500 and the monomer represented by formula 7 having a number average molecular weight of 600 are used. In another embodiment of the present invention, a monomer represented by formula 6 having a number average molecular weight of 1000 and a monomer represented by formula 8 having a number average molecular weight of 1000 are used.
In the invention, the ceramic electrolyte is selected from one or more of the electrolytes shown in formulas I to VI:
Li3+5xP1-xS4formula I; in the formula I, x is more than or equal to 0 and less than 1. Preferably, 0.1. ltoreq. x.ltoreq.0.9. In some embodiments of the invention, the electrolyte of formula I is Li3PS4And Li7P3S11One or more of them.
Li4-xGe1-xPxS4Formula II; in the formula II, x is more than 0 and less than 1. Preferably, 0.1. ltoreq. x.ltoreq.0.9. In some embodiments of the invention, the electrolyte of formula II is Li10GeP2S12。
Li10+xG1+xP2-xS12Formula III; in formula III, x is 1 or 2, and G is Si, Ge or Sn. Preferably, x is 1 and G is Si or Sn. In some embodiments of the invention, the electrolyte of formula III is Li11Si2PS12。
Li1+xMxTi2-x(PO4)3Formula IV; in the formula IV, x is more than 0 and less than 2, and M is Al, In, Ge, Ga, Y, Lu or La. Preferably, x is 0.1-1.8, and M is Al, In, Ge, Ga or La. In some embodiments of the invention, the electrolyte of formula IV is Li1.5Al0.5Ti1.5(PO4)3And Li1.4Al0.4Ti1.6(PO4)3One or more of them.
Li0.5-3xLa0.5+xTiO3Formula V; in the formula V, x is more than 0 and less than 0.15. Preferably, 0.01. ltoreq. x.ltoreq.0.145. In some embodiments of the inventionIn the examples, the electrolyte of formula V is Li0.33La0.557TiO3。
Li7-xLa3Zr2-xMxO12Formula VI; in the formula VI, x is more than or equal to 0 and less than or equal to 2, and M is Zr, Hf, Sn, Nb, Y, W or Ta. Preferably, x is 0-1, and M is Zr, Sn, Nb or W. In some embodiments of the invention, the electrolyte of formula VI is Li7La3Zr2O12And Li6.4La3Zr1.4Ta0.6O12One or more of them. The ceramic-type electrolyte of the present invention is not particularly limited in its source, and may be generally commercially available or obtained according to a conventional preparation method for preparing a ceramic-type electrolyte, which is well known to those skilled in the art.
In the present invention, the average particle diameter of the ceramic electrolyte is preferably 5 to 500nm, and more preferably 30 to 400 nm. In some embodiments of the invention, the ceramic-type electrolyte has an average particle size of 100nm, 200nm, 250nm, 300nm, or 320 nm. The ceramic type electrolyte powder may be preferably milled in advance to achieve the above particle diameter before mixing. In the present invention, the grinding method is not particularly limited, and may be a conventional grinding method known to those skilled in the art, such as ball milling.
According to the invention, the specific polymer monomer is combined with the ceramic electrolyte, the ceramic electrolyte particles are uniformly dispersed in the polymer monomer, and in the in-situ curing and forming process, the polymer monomer is polymerized to form a new polymer which is uniformly and fully contacted with the ceramic electrolyte particles, so that the ionic conductivity of the electrolyte material is improved under the synergistic effect.
In the present invention, the lithium salt is preferably LiN (CF)3SO2)2、LiN(FSO2)2、LiClO4、LiCF3SO3、LiBF4、LiPF4、LiAsF6And LiB (C)2O4)2One or more of them. More preferably LiN (CF)3SO2)2、LiClO4And LiCF3SO3One or more of them. The present invention is free of sources of said lithium saltsWith specific limitation, the compound is generally commercially available or can be prepared according to a preparation method well known to those skilled in the art.
In the present invention, the raw materials are preferably used in the following amounts in parts by mass:
0.1-60 parts of a polymer monomer;
1-99.9 parts of ceramic electrolyte;
1-99.9 parts of lithium salt.
More preferably, the amounts are as follows:
5-40 parts of a polymer monomer;
20-70 parts of a ceramic electrolyte;
5-70 parts of lithium salt.
In some embodiments of the invention, the polymer monomer is used in an amount of 5 parts, 15 parts, 17.5 parts, 20 parts, or 30 parts. In some embodiments of the invention, the ceramic-type electrolyte is used in an amount of 55 parts, 70 parts, 75 parts, 80 parts, or 90 parts. In some embodiments of the invention, the lithium salt is used in an amount of 5 parts, 10 parts, or 15 parts.
In some embodiments of the invention, an initiator and/or a catalyst is also added in step a). The initiator is preferably a thermal initiator or a photoinitiator. The thermal initiator is preferably one or more of azobisisobutyronitrile, tert-butyl hydroperoxide, dibenzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, tert-butyl peroxypivalate and hydrogen peroxide. The photoinitiator is preferably one or more of benzoin, benzoin ethyl ether, benzoin butyl ether, benzoin dimethyl ether, 2-hydroxy-2-methyl-1-phenyl ketone and benzophenone. The catalyst is preferably one or more of triethanolamine, tetramethylguanidine, trimethylene diamine, 1-methylimidazole, 2-phenylimidazole and 2-undecylimidazole. The mass ratio of the initiator and/or catalyst to the total amount of the polymer monomer, the ceramic electrolyte and the lithium salt is preferably 0.1-2% based on 100 parts by mass.
In the present invention, in the step a), the raw materials are mixed without using a solvent, i.e., under a non-solvent condition. In the invention, the mixing mode is preferably one or more of mechanical stirring, ultrasonic dispersion, ball milling and roller milling. The temperature of the mixing is not particularly limited, and may be carried out at room temperature. The mixing time is preferably 2-24 h. The mixing is preferably carried out under an inert atmosphere; the inert gas used in the present invention for providing the inert atmosphere is not particularly limited, and may be any conventional inert gas known to those skilled in the art, such as nitrogen or argon. After mixing, an electrolyte slurry is obtained.
According to the invention, after the electrolyte slurry is obtained, the electrolyte slurry is coated on the positive plate and is cured and formed in situ to obtain the integrated material.
In the invention, the coating mode is preferably one or more of blade coating, casting, spin coating and spray coating.
In the invention, the positive electrode material of the positive plate is preferably one or more of nickel cobalt lithium manganate, nickel cobalt lithium aluminate, nickel cobalt lithium, lithium cobalt oxide, nickel lithium phosphate and cobalt lithium phosphate.
In the present invention, the in-situ curing molding is preferably thermal curing molding or ultraviolet curing molding. Wherein the temperature for thermosetting molding is preferably 40-200 ℃; the time for thermosetting molding is preferably 2-24 h. The time for ultraviolet curing is preferably 0.5-2 h. After the slurry is coated on the positive plate, the electrolyte material can enter the pores of the positive electrode to form three-dimensional contact, and the composite electrolyte is formed on the positive plate through in-situ curing, so that the charge transfer impedance can be reduced. The structure of the composite electrolyte is shown in fig. 1, and fig. 1 is a schematic structural diagram of the electrolyte-cathode integrated material formed by in-situ curing, and it can be seen that the polymer composite electrolyte formed by in-situ curing is fully contacted with the cathode material particles, and the electrolyte and the cathode material particles form an integrated structure.
In the present invention, the thickness of the electrolyte layer in the integrated material is preferably 3 to 500. mu.m. In some embodiments of the invention, the electrolyte layer has a thickness of 10 μm, 15 μm, 20 μm, 50 μm, 100 μm or 110 μm.
The invention also provides a lithium metal battery which comprises the in-situ forming polymer composite electrolyte-anode integrated material and the cathode in the technical scheme. In the present invention, the negative electrode is preferably a metallic lithium negative electrode.
The in-situ forming polymer composite electrolyte-anode integrated material prepared by the invention has the following beneficial effects:
(1) the preparation process is carried out under the condition of no solvent, so that the solvent removal procedure is omitted, the problem that the solvent is difficult to remove is solved, and the influence of the solvent on the electrolyte and the battery performance is avoided.
(2) The solvent-free slurry containing the specific polymer monomer is directly coated on the positive plate, can enter pores of the positive plate and form three-dimensional contact with a positive material, and is formed in situ on the positive plate, so that the charge transfer impedance is reduced. The test result shows that the charge transfer impedance is 175 omega-m2The following.
(3) A specific polymer monomer is adopted, a new polymer is polymerized in the curing and forming process, and the new polymer and the ceramic electrolyte have synergistic effect, so that the whole electrolyte material has high lithium ion conductivity. The test result shows that the ionic conductivity is 1.5 multiplied by 10- 5And more than S/cm.
(4) The lithium metal battery is assembled by using the material with the integrated structure prepared by the special preparation process, so that the battery has excellent electrochemical performance. Test results show that the electrochemical window of the battery reaches 0-6V, and the capacity retention rate after 500 cycles reaches more than 70%.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
1.1 sample preparation
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the speed of 200rpm at room temperature10GeP2S12Grinding to obtain particles with average particle diameter of 320 nm.
S2, under the protection of argon atmosphere30 parts of a polymer monomer (represented by formula 1, Mn ═ 1000g/mol), 0.3 part of photoinitiator benzoin, and 15 parts of LiCF3SO355 parts of Li10GeP2S12And mixing the nano particles for 6 hours at room temperature by using a high-energy ball mill to obtain electrolyte slurry.
S3, directly coating the obtained electrolyte slurry on a nickel cobalt lithium manganate positive electrode sheet by scraping, and carrying out ultraviolet curing for 1h to carry out in-situ forming to obtain the electrolyte-positive electrode integrated material, wherein the thickness of the electrolyte layer is 50 μm.
1.2 Performance testing
(1) And assembling the obtained integrated material and a lithium metal negative electrode into a lithium metal battery. Carrying out electrochemical impedance spectrum test, linear sweep voltammetry test and cyclic charge and discharge test on the lithium metal battery; wherein, the test conditions of cyclic charge and discharge are as follows: 0.5C, capacity retention after 500 cycles of the test.
The test results are: the charge transfer resistance of the electrode/electrolyte was 70. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 77%.
(2) And (4) coating the electrolyte slurry obtained in the step S2) on a glass plate by scraping, and carrying out ultraviolet curing molding. And (3) carrying out electrochemical impedance spectrum test on the formed electrolyte at room temperature, wherein the blocking electrodes on two sides are respectively stainless steel. The results showed that the lithium ion conductivity was 5.5X 10-3S/cm。
Example 2
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the speed of 300rpm at room temperature7La3Zr2O12Grinding to obtain particles with average particle diameter of 300 nm.
S2 was prepared by mixing 20 parts of a polymer monomer (represented by formula 2, Mn 1500g/mol) and 5 parts of LiN (CF) under an argon atmosphere3SO2)275 parts of Li7La3Zr2O12And mixing the nano particles at room temperature for 6 hours by mechanical stirring and ultrasonic dispersion to obtain the electrolyte slurry.
S3, directly coating the obtained electrolyte slurry on a nickel-cobalt lithium aluminate anode plate by scraping, and then thermally curing at 110 ℃ for 2h to obtain an electrolyte-anode integrated material, wherein the thickness of the electrolyte layer is 50 μm.
1.2 Performance testing
The performance tests were carried out according to the test method of example 1, and the results show that: the charge transfer resistance of the electrode/electrolyte was 100. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 82%; lithium ion conductivity 2.2X 10-4S/cm。
Example 3
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the speed of 350rpm at room temperature1.5Al0.5Ti1.5(PO4)3Grinding to obtain particles with average particle diameter of 300 nm.
S2, under an argon atmosphere, 3 parts of polymer monomer 1 (represented by formula 2, Mn ═ 1500g/mol), 2 parts of polymer monomer 2 (represented by formula 3, Mn ═ 1000g/mol), and 5 parts of LiClO490 parts of Li1.5Al0.5Ti1.5(PO4)3And mixing the nano particles at room temperature for 6 hours by roller milling and ultrasonic dispersion to obtain electrolyte slurry.
S3, directly spraying the obtained electrolyte slurry on a lithium nickel cobalt oxide positive electrode sheet, and then thermally curing at 100 ℃ for 12h to obtain the electrolyte-positive electrode integrated material, wherein the thickness of the electrolyte layer is 10 μm.
1.2 Performance testing
The performance tests were carried out according to the test method of example 1, and the results show that: the charge transfer resistance of the electrode/electrolyte was 110. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 70%; lithium ion conductivity 1.5X 10-4S/cm。
Example 4
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the speed of 300rpm at room temperature3PS4Grinding to obtain particles with average particle diameter of 100 nm.
S2 is prepared by mixing 15 parts of a polymer monomer (represented by formula 4, Mn 1200g/mol), 0.2 part of azobisisobutyronitrile (aibn), and 5 parts of LiN (FSO) under an argon atmosphere2)280 parts of Li3PS4Nanoparticle medicineAnd mixing the roll mill and the ultrasonic dispersion for 6 hours at room temperature to obtain electrolyte slurry.
S3, directly casting the obtained electrolyte slurry on a lithium cobaltate positive electrode sheet, and then thermally curing at 110 ℃ for 2h to obtain the electrolyte-positive electrode integrated material, wherein the thickness of the electrolyte layer is 100 μm.
1.2 Performance testing
The performance tests were carried out according to the test method of example 1, and the results show that: the charge transfer resistance of the electrode/electrolyte was 160. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 80%; lithium ion conductivity 1.2X 10-4S/cm。
Example 5
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the speed of 300rpm at room temperature1.4Al0.4Ti1.6(PO4)3Grinding into particles with an average particle size of 250 nm.
S2, under an argon atmosphere, 15 parts of polymer monomer 1 (represented by formula 2, Mn ═ 1500g/mol), 5 parts of polymer monomer 2 (represented by formula 5, Mn ═ 500g/mol), 0.02 part of catalyst triethanolamine, and 10 parts of LiBF470 parts of Li1.4Al0.4Ti1.6(PO4)3And (3) mixing the nano particles for 6 hours at room temperature by high-energy ball milling to obtain electrolyte slurry.
S3, directly spin-coating the obtained electrolyte slurry on a lithium nickel phosphate positive plate, and then thermally curing at 150 ℃ for 12h to obtain the electrolyte-positive plate integrated material, wherein the electrolyte layer is 20 μm thick.
1.2 Performance testing
The performance tests were carried out according to the test method of example 1, and the results show that: the charge transfer resistance of the electrode/electrolyte was 90. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 79%; lithium ion conductivity 1.5X 10-4S/cm。
Example 6
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the rotating speed of 250rpm at room temperature0.33La0.557TiO3Ground to an average particle size of 300nmAnd (3) granules.
S2, 10 parts of polymer monomer 1 (represented by formula 2, Mn: 1500g/mol), 5 parts of polymer monomer 2 (represented by formula 6, Mn: 1000g/mol), and 5 parts of LiPF were added under an argon atmosphere480 parts of Li0.33La0.557TiO3And mixing the nano particles at room temperature for 6 hours by mechanical stirring and ultrasonic dispersion to obtain the electrolyte slurry.
S3, directly coating the obtained electrolyte slurry on a lithium cobalt phosphate positive electrode sheet by scraping, and then thermally curing at 80 ℃ for 12h to obtain the electrolyte-positive electrode integrated material, wherein the thickness of the electrolyte layer is 50 μm.
1.2 Performance testing
The performance tests were carried out according to the test method of example 1, and the results show that: the charge transfer resistance of the electrode/electrolyte was 155. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 82%; lithium ion conductivity 1.5X 10-5S/cm。
Example 7
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the rotating speed of 250rpm at room temperature7P3S11Grinding to obtain particles with average particle diameter of 100 nm.
S2, 10 parts of polymer monomer 1 (represented by formula 2, Mn: 1500g/mol), 5 parts of polymer monomer 2 (represented by formula 7, Mn: 600g/mol), and 10 parts of LiAsF were added under an argon atmosphere675 parts of Li7P3S11And mixing the nano particles at room temperature for 6 hours by mechanical stirring and ultrasonic dispersion to obtain the electrolyte slurry.
S3, directly spin-coating the obtained electrolyte slurry on a nickel cobalt lithium manganate positive electrode sheet, and then thermally curing at 80 ℃ for 12h to obtain an electrolyte-positive electrode integrated material, wherein the thickness of an electrolyte layer is 15 microns.
1.2 Performance testing
The performance tests were carried out according to the test method of example 1, and the results show that: the charge transfer resistance of the electrode/electrolyte was 77. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 86%; lithium ion conductivity 9.6X 10-4S/cm。
Example 8
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the speed of 300rpm at room temperature6.4La3Zr1.4Ta0.6O12Grinding to obtain particles with average particle diameter of 300 nm.
S2 was prepared under an argon atmosphere by mixing 3.5 parts of polymer monomer 1 (shown in formula 2, Mn ═ 1500g/mol), 1.5 parts of polymer monomer 2 (shown in formula 6, Mn ═ 1000g/mol), and 5 parts of LiB (C)2O4)290 parts of Li6.4La3Zr1.4Ta0.6O12And mixing the nano particles at room temperature for 6 hours by mechanical stirring and ultrasonic dispersion to obtain the electrolyte slurry.
S3, directly coating the obtained electrolyte slurry on a nickel-cobalt lithium aluminate anode plate by scraping, and then thermally curing at 80 ℃ for 12h to obtain the electrolyte-anode integrated material, wherein the thickness of the electrolyte layer is 50 μm.
1.2 Performance testing
The performance tests were carried out according to the test method of example 1, and the results show that: the charge transfer resistance of the electrode/electrolyte was 175. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 79%; lithium ion conductivity 1.7X 10-4S/cm。
Example 9
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the speed of 300rpm at room temperature11Si2PS12Grinding into particles with an average particle size of 200 nm.
S2, 10 parts of polymer monomer 1 (represented by formula 6, Mn ═ 1000g/mol), 7.5 parts of polymer monomer 2 (represented by formula 8, Mn ═ 1000g/mol), and 10 parts of LiAsF were mixed under an argon atmosphere675 parts of Li11Si2PS12And (3) mixing the nano particles for 6 hours at room temperature by high-energy ball milling to obtain electrolyte slurry.
S3, directly casting the obtained electrolyte slurry on a lithium nickel cobaltate positive electrode sheet, and then thermally curing at 60 ℃ for 6 hours to obtain the electrolyte-positive electrode integrated material, wherein the thickness of the electrolyte layer is 110 microns.
1.2 Performance testing
The performance tests were carried out according to the test method of example 1, and the results show that: the charge transfer resistance of the electrode/electrolyte was 140. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 87%; lithium ion conductivity 2.6X 10-4S/cm。
Example 10
S1, using a high-energy ball mill to rotate the ceramic electrolyte Li at the speed of 300rpm at room temperature1.5Al0.5Ti1.5(PO4)3Grinding into particles with an average particle size of 250 nm.
S2 is prepared by mixing 15 parts of a polymer monomer (represented by formula 4, Mn 1200g/mol), 0.2 part of a thermal initiator dibenzoyl peroxide, and 5 parts of LiN (FSO) under an argon atmosphere2)280 parts of Li1.5Al0.5Ti1.5(PO4)3And (3) mixing the nano particles for 6 hours at room temperature by high-energy ball milling to obtain electrolyte slurry.
S3, directly coating the obtained electrolyte slurry on a lithium cobaltate positive electrode sheet by scraping, and then thermally curing at 110 ℃ for 2h to obtain the electrolyte-positive electrode integrated material, wherein the thickness of the electrolyte layer is 100 μm.
1.2 Performance testing
The performance tests were carried out according to the test method of example 1, and the results show that: the charge transfer resistance of the electrode/electrolyte was 150. omega. m2The electrochemical window is 0-6V, and the capacity retention rate is 88%; lithium ion conductivity 1.2X 10-4S/cm。
Comparative example 1
The procedure was followed as in example 8, except that in step S2, 400 parts of N, N-dimethylformamide solvent was added; in step S3, the positive electrode sheet is not directly coated and formed, but a glass substrate is coated and formed.
After obtaining an electrolyte material, the electrolyte material was assembled with the positive electrode sheet and the negative electrode sheet in example 8 to form a lithium metal battery.
The performance of the metal batteries was tested according to the test method of example 8, and the results showed that: the charge transfer resistance of the electrode/electrolyte was 730. omega. m2Electrochemical methodThe chemical window is 0-4.5V, and the capacity retention rate is 55%. Compared with example 8, each property is obviously reduced; the mode of preparation and in-situ forming under the non-solvent condition of the invention proves that the electrochemical performance of the material can be obviously improved.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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