CN114566704A - Preparation method of semisolid gel electrolyte - Google Patents
Preparation method of semisolid gel electrolyte Download PDFInfo
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- CN114566704A CN114566704A CN202210197917.XA CN202210197917A CN114566704A CN 114566704 A CN114566704 A CN 114566704A CN 202210197917 A CN202210197917 A CN 202210197917A CN 114566704 A CN114566704 A CN 114566704A
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Abstract
The invention relates to a preparation method of a semi-solid gel electrolyte. The preparation method comprises the following steps: dissolving nitrate in an organic solvent, mixing with PVP, PAN or PVA solution, preparing a fiber film through high-voltage electrostatic spinning, and then carrying out high-temperature hot-pressing sintering on the fiber film to obtain a fast ion conductor with a continuous structure; and then pouring a PEO, PVA or PAN solution on the surface of the fast ion conductor, drying and then soaking in an electrolyte to obtain the semi-solid fast ion conductor gel electrolyte. The gel electrolyte prepared by the invention can improve the ionic conductivity in the semi-solid electrolyte.
Description
Technical Field
The invention belongs to the field of electrolyte, particularly relates to a preparation method of a semi-solid gel electrolyte, and particularly relates to a preparation method of semi-solid gel electrolyte diaphragm slurry.
Background
The solid electrolyte has high mechanical property and high stability, and provides possibility for the development of next-generation safe and high-energy storage batteries. Compared with a liquid electrolyte, the solid electrolyte has the following outstanding advantages: firstly, the solid electrolyte has no leakage problem, is stably contacted with air, and has no burning and explosion danger. Secondly, the solid electrolyte battery is easy to form a film, easy to laminate and low in packaging difficulty, and high-voltage integration and large-scale production are easy to realize. In addition, compared with the electrolyte, most of the electrolyte has higher lithium ion migration number, and the concentration polarization problem of the battery can be effectively solved. In many solid electrolytes, the ionic conductivity is generally lower than that of conventional liquid electrolytes.
In the prior art, the fast ion conductors are dispersed particles and cannot form a complete ion conduction network. The prior patent CN113644377A describes a semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry and a preparation method and application thereof; the used fast ion conductor lithium titanium phosphate is granular; the ionic conductivity is only 2.9ms/cm, which is lower than that of the traditional liquid electrolyte, namely 10 ms/cm. The invention provides a method for improving ionic conductivity by constructing a fast ionic conductor gel semisolid electrolyte with a continuous structure. Prior patent CN201811181826, relying only on PEO and lithium bistrifluoromethylsulfonylamide (LITFSI) as 10: 1 is higher than the EIS impedance of a gel electrolyte membrane obtained by soaking and sintering a membrane obtained by dissolving a gel solution obtained in acetonitrile, and the ionic conductivity is poorer.
Disclosure of Invention
The invention aims to provide a preparation method of a semi-solid gel electrolyte aiming at the problem of low ionic conductivity in the semi-solid electrolyte.
The fast ion conductor prepared by the invention is a 3D network structure with a continuous structure. During pouring, the surface of the fast ion conductor is covered by the polymer solution to form a polymer film which is wrapped and permeated into the structure of the fast ion conductor, and the polymer film can be subsequently soaked, washed and absorbed with electrolyte to form gel and protect the fast ion conductor with the relatively fragile and continuous structure in the 3D network structure. The polymer film and the 3D network structure fast ion conductor with the continuous structure are provided with abundant pore structures and can absorb liquid and swell into gel electrolyte after being soaked in electrolyte.
The purpose of the invention can be realized by the following scheme:
the invention provides a preparation method of a semi-solid gel electrolyte, which comprises the following steps:
s1, dissolving nitrate in an organic solvent 1 to obtain a solution A;
s2, dissolving the polymer powder 1 in an organic solvent 1, and stirring to obtain a solution B;
s3, adding the solution A into the solution B, and stirring to obtain a solution C;
s4, preparing the solution C obtained in the step S3 into a fiber film, and then carrying out hot-pressing sintering on the fiber film to obtain a fast ion conductor with a continuous structure;
s5, adding the polymer powder 2 into the organic solvent 2; uniformly mixing and stirring to obtain a solution D, pouring the solution D on the surface of the fast ion conductor obtained in the step S4, and drying to obtain a dried substance;
and S6, soaking the dried substance obtained in the step S5 in an electrolyte to obtain the semi-solid gel electrolyte.
As an embodiment of the present invention, the organic solvent 1 includes at least one of three organic solvents including DMF, NMP, and acetonitrile, and the organic solvent 1 includes DMF. The nitrate comprises one or more of zirconium nitrate, lithium nitrate and lanthanum nitrate.
As an embodiment of the present invention, the nitrate salts include lithium nitrate, lanthanum nitrate, and zirconium nitrate. Lithium: lanthanum: the stoichiometric ratio of zirconium elements is (70-75): (30-40); (10-20).
In one embodiment of the present invention, in step S2, the polymer powder 1 includes one of PVP, PAN, and PVA.
As an embodiment of the present invention, the stirring in step S2 is magnetic stirring, and the stirring time is 3-4 h.
In one embodiment of the present invention, the stirring in step S3 is magnetic stirring, and the stirring time is 12 to 24 hours.
As an embodiment of the present invention, the fiber film in step S4 is manufactured by a high voltage electrospinning device. The technological parameters of the high-voltage electrostatic spinning equipment are as follows: the distance between the spinning needle head and the material receiving winding drum is 10-20 cm; the positive and negative voltage difference is 20-25 kv, the spinning speed is 0.5-2 ml/h, and the ambient temperature is 25 +/-3 ℃; the humidity is 20-40%.
As an embodiment of the present invention, the temperature of the high temperature hot press sintering in step S4 is 700 ℃. + -. 50 ℃ and the time is 7. + -. 2 h. The hot-pressing sintering is obtained by placing the ceramic flat plate in a hot-pressing sintering way. The sintering pressure is 3 +/-0.5 kpa. The product obtained by sintering at the temperature lower than 650 ℃ has lower crystallinity, the sintering temperature is higher than 750 ℃ or the pressure of a ceramic flat plate is higher than 3.5kpa, the continuous structure of the obtained fast ion conductor solid electrolyte can be damaged, and the brittleness is increased. When the pressure of the ceramic flat plate is less than 2.5kpa, the fiber film shrinks greatly at high temperature, the flatness of the obtained conductor cannot be maintained, and the subsequent pouring and the preparation of gel electrolyte are not facilitated. When the sintering time is shorter than 5h, the material is not decomposed and crystallized sufficiently, a fast conductor with higher crystallinity cannot be synthesized, and when the sintering temperature is longer than 9h, the sintering time is too long, the product crystal grains are larger, the material brittleness is higher, the subsequent pouring is not facilitated, and the preparation of the gel electrolyte with better flatness is not facilitated
In an embodiment of the present invention, the polymer powder 2 in step S5 includes one of PEO, PVA, and PAN.
As an embodiment of the present invention, the organic solvent 2 in step S5 includes one of acetone and acetonitrile.
As an embodiment of the present invention, the stirring time in step S5 is 3 hours.
As an embodiment of the present invention, the temperature of the drying in step S5 is 30 ± 5 ℃; the drying time is 12-24 h.
As an embodiment of the present invention, the soaking time in step S6 is 24-36 h.
The hot-pressing sintering treatment can ensure that the fiber membrane does not shrink violently in the heat treatment process, thereby ensuring the smoothness and the non-fragmentation of the structure. If the polymer film obtained by spinning is not subjected to hot-pressing sintering, the polymer film is only used as a carrier for subsequent growth, and the polymer film does not have rich hole structures, so that the obtained gel electrolyte film is weak in ion conducting capacity. The fibers after hot-pressing sintering are long fibers, and the whole body is a fast ion conductor, so that the ion conduction capability is stronger.
Compared with the prior art, the invention has the following beneficial effects:
1. the ion conductivity of the semisolid gel network-shaped fast ion conductor electrolyte is up to 6 x 10-3s/cm, and the ion conductivity of the conventional granular fast ion conductor filled gel electrolyte is only 2 x 10-3s/cm。
2. The structurally continuous fast ion conductor structure provides continuous and multiple channels for lithium ion transport.
3. The gel electrolyte swelled by soaking the electrolyte reduces the interface impedance between the electrolyte and the active material of the pole piece.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is a schematic structural view of a fast ion conductor after casting in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples, which are set forth to provide a detailed description of the invention and a detailed description of the operation, will help those skilled in the art to further understand the present invention. It should be noted that the scope of the present invention is not limited to the following embodiments, and that several modifications and improvements made on the premise of the idea of the present invention belong to the scope of the present invention.
The semi-solid gel electrolyte prepared by the invention is used for testing the ionic conductivity of the electrolyte by the following method:
step a, manufacturing a semi-solid electrolyte membrane into an electrolyte round sheet in an anhydrous and oxygen-free environment;
b, placing the semi-solid electrolyte membrane wafer in the step a in a tripolar cell testing device, wherein positive and negative electrodes are stainless steel electrodes;
c, performing alternating current impedance test on the solid-state battery by using an electrochemical workstation to obtain an EIS curve of the semisolid electrolyte membrane, and reading the impedance value of the semisolid electrolyte membrane from the EIS curve;
step d, according to the impedance value of the solid electrolyte,
by the formula: calculating sigma-L/RS to obtain the conductivity of the solid electrolyte;
wherein σ is the conductivity (S/cm) of the semi-solid electrolyte membrane;
s is the area (cm) of the semisolid electrolyte membrane2)；
L is the thickness (cm) of the semi-solid electrolyte membrane;
r is a semi-solid electrolyte membrane impedance value (Ω) obtained from the ac impedance diagram.
Example 1
The embodiment provides a preparation method of a semi-solid gel electrolyte, which comprises the following steps:
step 1, dissolving lithium nitrate, lanthanum nitrate and zirconium nitrate in NMP, and mixing the components according to the proportion of lithium: lanthanum: the stoichiometric ratio of zirconium was 7:3:2, and the zirconium was dissolved in NMP at a ratio of nitrate to NMP of 1 g: 20ml, magnetically stirring for 3 hours to obtain a clear solution A;
step 2, dissolving high polymer powder PVP in NMP, wherein the dosage ratio is 4 g: 20ml, and obtaining a clear solution B after magnetically stirring for 3 hours;
and 3, slowly dropwise adding the solution A into the solution B, wherein the volume ratio is 1: 20, magnetically stirring for 12 hours to obtain a clear solution C;
step 4, placing the solution C in electrostatic spinning equipment for high-voltage electrostatic spinning, wherein the working parameter of the equipment is that the distance between a spinning needle and a material receiving winding drum is 20 cm; the positive and negative voltage difference is 23kv, the spinning speed is 1ml/h, and the ambient temperature is 25 ℃; the humidity is 30%;
step 5, placing the spinning fiber membrane obtained in the step 4 in a ceramic flat plate, and performing hot-pressing sintering to obtain a fast ion conductor with a continuous structure, wherein the obtained product is shown in figure 1, and the ceramic plate pressure is 3 kpa; the sintering temperature is 700 ℃; the sintering time is 6 h.
Step 6, dissolving the high polymer powder PEO in an organic solvent acetone according to the dosage ratio of 3 g: 10ml, stirring for 3 hours to obtain transparent clear liquid D, subsequently pouring the transparent clear liquid D on the surface of the fast ion conductor with the continuous structure obtained in the step 5, and drying for 12 hours at the temperature of 30 ℃;
and 7, soaking the dried substance obtained in the step 6 in an electrolyte (volume ratio V (EC): V (EMC): V (DMC): 1:1: 1; 1mol/L LiPF6) for 24 hours to obtain the semi-solid gel fast ion conductor electrolyte.
Step 8; step 7, the conductivity of the semi-solid gel fast ionic conductor electrolyte is tested. The prepared semi-solid gel network-shaped fast ion conductor electrolyte has ion conductivity as high as 6.2 x 10-3s/cm。
Example 2
The embodiment provides a preparation method of a semi-solid gel electrolyte, which comprises the following steps:
step 1, dissolving lithium nitrate, lanthanum nitrate and zirconium nitrate in NMP, and mixing the components according to the proportion of lithium: lanthanum: zirconium was weighed at a stoichiometric ratio of 7:3:2, dissolved in NMP at a ratio of nitrate to NMP of 1 g: 20ml, magnetically stirring for 3 hours to obtain a clear solution A;
and 2, dissolving high polymer powder PVP in NMP, wherein the dosage ratio is 4 g: 20ml, magnetically stirring for 3 hours to obtain a clear solution B;
and 3, slowly dropwise adding the solution A into the solution B, wherein the volume ratio is 1: 20, magnetically stirring for 12 hours to obtain a clear solution C;
step 4, placing the solution C in electrostatic spinning equipment for high-voltage electrostatic spinning, wherein the working parameter of the equipment is that the distance between a spinning needle and a material receiving winding drum is 20 cm; the positive and negative voltage difference is 23kv, the spinning speed is 1ml/h, and the ambient temperature is 25 ℃; the humidity is 30%;
step 5, placing the spinning fiber membrane obtained in the step 4 in a ceramic flat plate, and performing hot-pressing sintering to obtain a fast ion conductor with a continuous structure, wherein the pressure of the ceramic plate is 2.8 kpa; the sintering temperature is 650 ℃; the sintering time is 5 h.
And 6, dissolving the high polymer powder PEO in an organic solvent acetone according to the dosage ratio of 3 g: 10ml, stirring for 3 hours to obtain a transparent clear liquid D, subsequently pouring the transparent clear liquid D on the surface of the fast ion conductor with the continuous structure obtained in the step 5, and drying for 12 hours at 30 ℃;
step 7, soaking the dried substance obtained in the step 6 in an electrolyte (volume ratio V (EC): V (EMC): V (DMC): 1:1: 1; 1mol/L LiPF6) for 24 hours to obtain a semisolid gel fast ion conductor electrolyte;
and 8, testing the conductivity of the semi-solid gel fast ionic conductor electrolyte in the step 7. The ionic conductivity of the semisolid gel network-shaped fast ion conductor electrolyte is as high as 5.5 x 10-3s/cm。
Example 3
The embodiment provides a preparation method of a semi-solid gel electrolyte, which comprises the following steps:
step 1, dissolving lithium nitrate, lanthanum nitrate and zirconium nitrate in acetonitrile, according to the proportion of lithium: lanthanum: zirconium is weighed with a stoichiometric ratio of 70:34:17, dissolved in acetonitrile, the ratio of nitrate to acetonitrile is 1 g: 20ml, and obtaining a clear solution A after magnetically stirring for 3 hours;
and 2, dissolving polymer powder PAN in acetonitrile, wherein the dosage ratio is 4 g: 20ml, magnetically stirring for 3 hours to obtain a clear solution B;
and 3, slowly dropwise adding the solution A into the solution B, wherein the volume ratio is 1: 20, magnetically stirring for 12 hours to obtain a clear solution C;
step 4, placing the solution C in electrostatic spinning equipment for high-voltage electrostatic spinning, wherein the working parameter of the equipment is that the distance between a spinning needle and a material receiving winding drum is 10 cm; the positive and negative voltage difference is 25kv, the spinning speed is 1.5ml/h, and the ambient temperature is 25 ℃; the humidity is 30%;
step 5, placing the spinning fiber membrane obtained in the step 4 in a ceramic flat plate, and performing hot-pressing sintering to obtain a fast ion conductor with a continuous structure, wherein the obtained product is shown in figure 1, and the ceramic plate pressure is 3 kpa; the sintering temperature is 750 ℃; the sintering time is 9 h.
And 6, dissolving the polymer powder PAN in an organic solvent acetone in a dosage ratio of 3 g: 10ml, stirring for 3 hours to obtain a transparent clear liquid D, subsequently pouring the transparent clear liquid D on the surface of the fast ion conductor with the continuous structure obtained in the step 5, and drying for 12 hours at 30 ℃;
and 7, soaking the dried substance obtained in the step 6 in an electrolyte (volume ratio V (EC): V (EMC): V (DMC): 1:1: 1; 1mol/L LiPF6) for 24 hours to obtain the semi-solid gel fast ion conductor electrolyte.
Step 8; step 7 conductivity of the semi-solid gel fast ionic conductor electrolyte is tested. The prepared semi-solid gel network-shaped fast ion conductor electrolyteIonic conductivity up to 5.0 x 10-3s/cm。
Comparative example 1
This comparative example provides a solid fast ion conductor electrolyte prepared essentially the same as example 1 except that: and (4) applying no pressure in the hot-pressing sintering process, and only performing sintering treatment.
The network fast ion conductor prepared by the embodiment has poor flatness and broken fibers because the fast ion conductor is not subjected to hot pressing treatment, and the ionic conductivity of the semi-solid gel network fast ion conductor electrolyte is 2.8 x 10-3s/cm。
Comparative example 2
This comparative example provides a solid fast ion conductor electrolyte prepared essentially the same as example 1 except that: fast ion conductors are different from conventional fillers.
Step 1, dissolving high molecular powder PEO in organic solvent 2 acetone, stirring for 3h to obtain transparent clear liquid D, and mixing with commercial SiO2D50 is 1um particle, and is mixed uniformly according to the mass ratio of 8:2, dried in a culture dish for 12h, and formed into a membrane.
Step 2, putting the dried substance obtained in the step 1 into an electrolyte (volume ratio V (EC): V (EMC): V (DMC): 1:1: 1; 1mol/L LiPF6) to be soaked for 24 hours to obtain a semisolid gel fast ion conductor electrolyte;
step 3; and (3) testing the conductivity of the semi-solid gel fast ion conductor electrolyte in the step 2.
The semi-solid gel network-shaped fast ion conductor electrolyte has the ion conductivity of 1.0 x 10-3s/cm。
Comparative example 3
This comparative example provides a solid fast ion conductor electrolyte prepared essentially the same as example 1 except that: the temperature of hot-pressing sintering is 500 ℃.
The semi-solid gel network-shaped fast ion conductor electrolyte has the ion conductivity of 1.3 x 10-3s/cm。
Comparative example 4
This comparative example provides a solid fast ion conductor electrolyte prepared essentially the same as example 1 except that: the pressure for hot press sintering was 6 kpa.
The semi-solid gel network-shaped fast ion conductor electrolyte has the ion conductivity of 2.5 x 10-3s/cm。
Comparative example 5
This comparative example provides a solid fast ion conductor electrolyte prepared essentially the same as example 1 except that: the time of hot-pressing sintering is 3 h.
The semi-solid gel network-shaped fast ion conductor electrolyte has the ion conductivity of 2.0 x 10-3s/cm。
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A method of preparing a semi-solid gel electrolyte, comprising the steps of:
s1, dissolving nitrate in an organic solvent 1 to obtain a solution A;
s2, dissolving the polymer powder 1 in an organic solvent 1, and stirring to obtain a solution B;
s3, adding the solution A into the solution B, and stirring to obtain a solution C;
s4, preparing the solution C obtained in the step S3 into a fiber film, and then carrying out hot-pressing sintering on the fiber film to obtain a fast ion conductor with a continuous structure;
s5, adding the polymer powder 2 into an organic solvent 2; uniformly mixing and stirring to obtain a solution D, pouring the solution D on the surface of the fast ion conductor obtained in the step S4, and drying to obtain a dried substance;
and S6, soaking the dried substance obtained in the step S5 in an electrolyte to obtain the semi-solid gel electrolyte.
2. The method according to claim 1, wherein the organic solvent 1 comprises at least one of DMF, NMP and acetonitrile.
3. The preparation method according to claim 1, wherein the nitrate in step S1 includes one or more of zirconium nitrate, lithium nitrate and lanthanum nitrate.
4. The method according to claim 1, wherein the polymer powder 1 in step S2 includes one of PVP, PAN, and PVA.
5. The method of claim 1, wherein the fiber film is prepared by a high voltage electrospinning device in step S4.
6. The preparation method according to claim 5, wherein the process parameters of the high-voltage electrostatic spinning equipment are as follows: the distance between the spinning needle head and the material receiving winding drum is 10-20 cm; the positive and negative voltage difference is 20-25 kv, the spinning speed is 0.5-2 ml/h, and the ambient temperature is 25 +/-3 ℃; the humidity is 20-40%.
7. The method according to claim 1, wherein the hot press sintering in step S4 is carried out at 700 ℃ ± 50 ℃ for 7 ± 2 hours.
8. The production method according to claim 1, wherein the pressure of the hot press sintering in step S4 is 3 ± 0.5 kpa.
9. The method according to claim 1, wherein the polymer powder 2 in step S5 includes one of PEO, PVA, and PAN.
10. The method according to claim 1, wherein the organic solvent 2 in step S5 includes one of acetone and acetonitrile.
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