CN116031479B - Polymer solid electrolyte slurry and film for lithium ion battery, preparation method and application - Google Patents
Polymer solid electrolyte slurry and film for lithium ion battery, preparation method and application Download PDFInfo
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- CN116031479B CN116031479B CN202310062556.2A CN202310062556A CN116031479B CN 116031479 B CN116031479 B CN 116031479B CN 202310062556 A CN202310062556 A CN 202310062556A CN 116031479 B CN116031479 B CN 116031479B
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Abstract
The invention relates to the field of solid lithium metal batteries, and discloses a polymer solid electrolyte slurry and a film of a lithium ion battery, a preparation method and application. The polymer solid electrolyte slurry consists of a continuous phase PVDF, a reinforcing phase pre-lithiated polyphenylene sulfide (PPS), lithium salt and an organic solvent; the single PVDF binder used in the process of manufacturing the battery core can be partially or completely replaced, so that the effects of increasing the lithium ion transmission efficiency, improving the interface contact and reducing the interface impedance are achieved. The polymer solid electrolyte membrane prepared based on the slurry improves the crystallinity of PVDF by adding pre-lithiated polyphenylene sulfide, and improves the mechanical property of the solid electrolyte membrane; the S-site channel on thioether bond is used for improving directional lithium ion migration and ionic conductivity, and meanwhile, the lithium ion rectification effect is achieved, and the growth of lithium dendrites is effectively inhibited.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and relates to a lithium ion battery polymer solid electrolyte slurry, a membrane, a preparation method and application.
Background
Solid-state lithium ion batteries have the application prospect of high energy density, small volume, safety, flexibility and deformability and are attracting attention.
The key material of solid state lithium ion batteries is a solid state electrolyte comprising a polymer system (conductivity 10 -7 -10 -5 S/cm), oxide system (conductivity 10 -6 -10 -3 S/cm), sulfide system (conductivity 10 -3 -10 -2 S/cm); compared with the conventional liquid electrolyte (conductivity 10 -2 S/cm) has a lower conductivity than the other. And when the lithium ion battery is applied to the battery core, the solid/solid interface contact area of the electrode and the electrolyte is small, the interface impedance is higher, and the transmission of lithium ions between interfaces is blocked, so that the problems of high impedance, poor power and unstable circulation of the solid lithium battery are directly caused, and the application of the solid lithium battery is limited.
The polymer solid electrolyte has better flexibility and workability, has good interface contact with an electrode, and can reduce the interface resistance of the solid battery; in addition, the low density of the materials, which can increase the energy density of the battery, is receiving increasing attention in all-solid-state lithium metal anode batteries. Common polymer solid electrolyte polyvinylidene fluoride (PVDF) polymers are valued for their stable electrochemical and mechanical properties and their ability to dissociate lithium salts well to increase their conductivity. But has higher crystallinity and high crystallization area ratio, so that lithium ions cannot be rapidly transmitted in the PVDF crystal structure, and the ion conductivity is poor at room temperature, namely about 10 -5 S·cm -1 The electrical conductivity is generally improved by gelling, which in turn leads to a decrease in mechanical properties. The solid electrolyte membrane based on PVDF-LiX has been reported to have a conductivity of 2.03X10 at room temperature of 25 ℃ −4 S cm −1 (X.Zhang, S.Wang, C.Xue, C.Xin, Y.Lin, Y.shen, L.Li, C. -W.Nan, adv. Mater.2019, 31, 1806082.). Although this has prompted the development of all solid state lithium metal batteries. However, the PVDF-based solid electrolyte membrane still has the problems of poor mechanical properties, thermal stability and compatibility with the electrode interface, and further improvement of the properties thereof is still required to meet the demands of commercial solid lithium battery production.
Disclosure of Invention
Aiming at the problems of poor interface contact, high solid/solid interface impedance, blocked transmission of lithium ions between interfaces, low room temperature ion conductivity, poor mechanical property and the like of PVDF-based solid electrolyte, the invention still has the requirements of high capacity, high energy density and high safety on the basis of improving the interface problem, and provides a single PVDF binder which can be used in the process of manufacturing a battery cell by partially or completely replacing the solid electrolyte slurry, thereby playing the roles of increasing the lithium ion transmission efficiency, improving the interface contact and reducing the interface impedance.
In addition, aiming at the problems of high crystallinity, low ionic conductivity and poor mechanical property of PVDF, the solid electrolyte membrane and the preparation method thereof are provided, and the crystallinity of PVDF is improved by adding pre-lithiated polyphenylene sulfide, so that the mechanical property of the solid electrolyte membrane is improved; the S-site channel on thioether bond is used for improving directional lithium ion migration and ionic conductivity, and meanwhile, the lithium ion rectification effect is achieved, and the growth of lithium dendrites is effectively inhibited.
And application of the solid electrolyte slurry and the solid electrolyte membrane in lithium ion secondary batteries.
The technical scheme of the invention is as follows:
the preparation method of the solid electrolyte slurry of the lithium ion battery polymer is characterized by comprising the following steps of:
step S1: preparing pre-lithiated polyphenylene sulfide powder, mixing polyphenylene sulfide particles, lithium chloride and a tetrachloro-p-benzoquinone anion complexing agent, placing the mixture in a reaction kettle of argon or nitrogen, heating to 200-400 ℃, reacting for 2-5 hours, then cooling to room temperature at a temperature of 1-2 ℃/min, washing the obtained product with deionized water for multiple times, filtering to neutrality, and vacuum-drying at 60 ℃ for 12-24 hours to obtain pre-lithiated polyphenylene sulfide powder A;
step S2: preparing polymer solid electrolyte slurry, namely premixing the pre-lithiated polyphenylene sulfide powder A obtained in the step S1 and polyvinylidene fluoride (PVDF) in a planetary mixer or a kneader for 1-2h, slowly adding an organic solvent until the solid content is 40-60%, and carrying out semi-dry kneading for 1-5h until the materials are uniformly kneaded; adding lithium salt, continuously kneading for 1-5h, then adding organic solvent until the solid content is 10-30%, and carrying out high-speed dispersion mixing, wherein the dispersion speed is 2000-5000 r/min, and the dispersion time is 1-2h, thus obtaining the solid electrolyte slurry B.
Further, the mass ratio of the polyphenylene sulfide to the lithium chloride to the tetrachloro-p-benzoquinone in the step S1 is 100:5-15:15-50.
Further, the dosage of the polyvinylidene fluoride (PVDF), the pre-lithiated polyphenylene sulfide powder A and the lithium salt is 40-50 parts by weight, 10-20 parts by weight and 20-40 parts by weight.
Further, the lithium salt is LiBF 4 And LiODFB, wherein LiBF is contained in the double salt 4 The mass ratio of LiODFB to the catalyst is 1:1-1.5.
Further, the organic solvent is one or more of N, N-dimethylformamide, tetrahydrofuran and N-methylpyrrolidone (NMP).
The solid electrolyte slurry of the ion battery polymer is prepared by the preparation method of the solid electrolyte slurry of the ion battery polymer.
The application of the polymer solid electrolyte slurry of the ion battery is characterized in that the binder used for the electrode plate of the battery is used for completely or partially replacing a single PVDF binder in the process of manufacturing the battery.
The method for preparing the solid electrolyte membrane of the lithium ion battery based on the solid electrolyte slurry is characterized in that a doctor blade coater is adopted to coat the solid electrolyte slurry B into a solid electrolyte membrane with the thickness of 25-50 mu m by using a tape casting method, and the solid electrolyte membrane is placed into a vacuum oven with the temperature of 60-100 ℃ to be dried for 10-24 hours, so that the solid electrolyte membrane C is finally obtained.
The solid electrolyte membrane of the lithium ion battery prepared by the method is characterized by comprising 40-50% by mass of continuous phase polyvinylidene fluoride (PVDF), 10-20% by mass of reinforced phase pre-lithiated polyphenylene sulfide (PPS), 20-40% by mass of lithium salt and 5-15% by mass of organic solvent.
Further, in the lithium ion battery polymer solid electrolyte membrane, the crystallinity of the continuous phase PVDF molecular structure is <72%; the linear crystallization area of the polyphenylene sulfide is more than 90%.
The application of the solid electrolyte membrane in preparing the battery core is characterized in that the solid electrolyte membrane is placed between a positive electrode and a negative electrode to manufacture a metal lithium negative electrode lithium ion battery or a non-negative electrode lithium ion battery.
Compared with the prior art, the invention has the following advantages
The prepared polymer solid electrolyte slurry can partially or completely replace PVDF binder, reduces contact resistance of electrode/electrolyte interface, reduces polarization internal resistance of battery, and has beneficial effects on circulation and stable performance of battery.
The addition of the enhancement phase pre-lithiated polyphenylene sulfide can improve the mechanical strength of the PVDF solid electrolyte membrane and enhance the ionic conductivity, and as the chelating agent of the pre-lithiated polyphenylene sulfide can chelate anions, concentration polarization is prevented, the directional migration of lithium ions along a sulfur (S) site channel is improved, and the lithium ion rectification effect is achieved, so that the growth of lithium dendrites is effectively inhibited.
The prepared polymer solid electrolyte membrane has the advantages of high decomposition voltage, large migration number of lithium ions and high ion conductivity, and can effectively improve the electrochemical performance of a lithium metal anode battery so as to meet the application requirements of commercial solid lithium batteries.
The method is simple, the film making process is simple, the film forming is fast, the efficiency is high, the conventional equipment is easy to control and operate, and therefore, the polymer solid electrolyte and the film can be prepared in a large scale, and the production requirement of commercial solid lithium batteries is met.
Drawings
FIG. 1 is a physical view of a polymer solid electrolyte membrane in example 1;
FIG. 2 is an SEM image of a polymer solid electrolyte membrane of example 1;
FIG. 3 is a graph of tensile properties of the polymer solid electrolyte of example 1;
FIG. 4 is a graph of the decomposition voltage (LSV) of the polymer solid electrolyte of example 1.
Description of the embodiments
The following examples are illustrative of the invention and are not to be construed as limiting the invention.
Examples
Firstly, 50g of polyphenylene sulfide particles, 5g of lithium chloride and 15g of tetrachloro-p-benzoquinone are mixed, placed in a reaction kettle which is continuously introduced with argon, heated to 220 ℃, reacted for 3 hours, then cooled to room temperature at a speed of 1 ℃ per minute, and the obtained product is washed with deionized water for many times, filtered to be neutral, and dried in vacuum at 60 ℃ for 20 hours to obtain the pre-lithiated polyphenylene sulfide powder A.
Polyvinylidene fluoride (PVDF) is put into an oven for drying at 80 ℃ for 24 hours, 50g of PVDF and 9.2g of pre-lithiated polyphenylene sulfide powder A are taken, premixed for 2 hours in a planetary mixer, 100 mL of N-methylpyrrolidone (NMP) is slowly added, semi-dry kneading is carried out for 2 hours, and then 33g of LiBF is added according to the mass ratio of 1:1.2 4 And LiODFB, continuously kneading for 2 hours, then adding 250 mL NMP as an organic solvent, setting the dispersion speed to 3000 r/min, and carrying out high-speed dispersion mixing for 1 hour to obtain the solid electrolyte slurry B.
The solid electrolyte slurry B was coated on a blade coater to form a film having a thickness of 30 μm, and then placed in a vacuum oven and dried at 100 ℃ for 24 hours to obtain a polymer solid electrolyte membrane C, see fig. 1. The surface of the solid electrolyte membrane can be observed using a scanning electron microscope SEM, see fig. 2, and it can be observed that PPS is uniformly distributed in the continuous phase of PVDF. Solid electrolyte membrane conductivity of 2.82×10 measured using ac impedance method -4 S/cm. The tensile strength was measured to be 6MPa by using an electronic universal tester, and is shown in FIG. 3, and the electrochemical window for the lithium sheet/solid electrolyte membrane/steel sheet half cell was measured to be 4.5V by using a linear voltammetry, and the linear voltammetry curve is shown in FIG. 4.
In the case, the button cell is adopted for electrochemical test, so that the solid electrolyte slurry B is adopted as a binder, and the preparation of the positive electrode plate is as follows: mixing an active substance LFP, solid electrolyte slurry B and conductive carbon super P according to the dry weight percentage of 94:2:4, adding an organic solvent NMP, putting into a grinding tank for grinding for 40 minutes, coating a positive plate with the single-sided thickness of 60 mu m on an aluminum foil of a knife coater, putting into an oven for drying at 60 ℃ for 2 hours, cutting into a positive plate with the diameter of 12mm by a sheet cutting machine, cutting into a lithium metal negative electrode with the diameter of 15mm by using the solid electrolyte membrane prepared in the embodiment as a diaphragm, and cutting into a solid electrolyte membrane with the diameter of 19 mm. After the positive plate is dried for 20 hours at the temperature of 100 ℃ in a vacuum oven, a solid electrolyte membrane is placed between a positive electrode and a negative electrode in a glove box, 5 mu L of lithium hexafluorophosphate commercial electrolyte is respectively added to the side of the positive electrode and the side of the negative electrode, the effect of wetting the plate is achieved, a button cell is assembled, and a 0.2C rate charge-discharge test is carried out on a charge-discharge tester, wherein the specific discharge capacity is 149mAh/g.
Examples 2-6 were prepared in the same manner as in example 1, except that the pre-lithiated polyphenylene sulfide, PVDF, lithium salt were in different proportions. The ratios of the pre-lithiated polyphenylene sulfide, PVDF, lithium salts of specific examples 2-6 are detailed in table 1.
Examples
Example 7 was prepared in the same manner as in example 2, except that the negative electrode was made of Cu which was not a negative electrode metal, specifically, a copper foil treated with phosphoric acid or nitric acid.
This comparative example is the same as the preparation method of the above example, except that the polymer electrolyte of PVDF and lithium salt, to which the pre-lithiated polyphenylene sulfide powder is not added.
The electrochemical performance comparisons of specific examples 1-7 and comparative examples are shown in Table 1.
TABLE 1 Polymer solid electrolyte compositions and electrochemical Properties of different examples
| Example composition | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Comparative example 1 |
| Negative electrode | Lithium sheet | Lithium sheet | Lithium sheet | Lithium sheet | Lithium sheet | Lithium sheet | Copper foil | Lithium sheet |
| PVDF | 50g | 50g | 50g | 50g | 50g | 60g | 50g | 50g |
| PPS | 9.2g | 14.7g | 20.75g | 9.2g | 14.7g | 14.7g | 14.7g | 0g |
| Li salt | 33g | 33g | 33g | 33g | 16.17g | 16.17g | 33g | 33g |
| Organic solvents | NMP | NMP | NMP | DMF | NMP | NMP | NMP | NMP |
| Specific discharge capacity of 0.2C | 149mAh/g | 150mAh/g | 140mAh/g | 148mAh/g | 145mAh/g | 145mAh/g | 150mAh/g | 137mAh/g |
Although embodiments of the present invention have been described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations may be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the lithium ion battery polymer solid electrolyte slurry is characterized by comprising the following steps:
step S1: preparing pre-lithiated polyphenylene sulfide powder, mixing polyphenylene sulfide particles, lithium chloride and a tetrachloro-p-benzoquinone anion complexing agent, placing the mixture in a reaction kettle of argon or nitrogen, heating to 200-400 ℃, reacting for 2-5 hours, then cooling to room temperature at a temperature of 1-2 ℃/min, washing the obtained product with deionized water for multiple times, filtering to neutrality, and vacuum-drying at 60 ℃ for 12-24 hours to obtain pre-lithiated polyphenylene sulfide powder A;
step S2: preparing polymer solid electrolyte slurry, namely premixing the pre-lithiated polyphenylene sulfide powder A obtained in the step S1 and polyvinylidene fluoride (PVDF) in a planetary mixer or a kneader for 1-2h, slowly adding an organic solvent until the solid content is 40-60%, and carrying out semi-dry kneading for 1-5h until the materials are uniformly kneaded; adding lithium salt, continuously kneading for 1-5h, then adding organic solvent until the solid content is 10-30%, and carrying out high-speed dispersion mixing, wherein the dispersion speed is 2000-5000 r/min, and the dispersion time is 1-2h, thus obtaining the solid electrolyte slurry B.
2. The method for preparing a solid electrolyte slurry according to claim 1, wherein the mass ratio of polyphenylene sulfide, lithium chloride and tetrachloro-p-benzoquinone in step S1 is 100:5-15:15-50; in the step S2, the dosage of the polyvinylidene fluoride (PVDF), the pre-lithiated polyphenylene sulfide powder A and the lithium salt is 40-50 parts by weight, 10-20 parts by weight and 20-40 parts by weight.
3. The method for producing a solid electrolyte slurry according to claim 1, wherein the lithium salt is LiBF 4 And LiODFB, wherein LiBF is contained in the double salt 4 With LiODFBThe mass ratio is 1:1-1.5.
4. The method for producing a solid electrolyte slurry according to claim 1, wherein the organic solvent is one or more of N, N-dimethylformamide, tetrahydrofuran, and N-methylpyrrolidone (NMP).
5. A lithium ion battery polymer solid electrolyte slurry prepared by the preparation method of any one of claims 1-4.
6. The use of the solid electrolyte slurry for lithium ion battery according to claim 5, wherein the binder for the electrode sheets in the process of manufacturing the cells completely or partially replaces the single PVDF binder.
7. The method for preparing the solid electrolyte membrane of the lithium ion battery based on the solid electrolyte slurry according to claim 5, wherein a doctor blade coater is adopted to coat the solid electrolyte slurry B into a solid electrolyte membrane with the thickness of 25-50 μm by using a tape casting method, and the solid electrolyte membrane is placed into a vacuum oven with the temperature of 60-100 ℃ to be dried for 10-24 hours, so that the solid electrolyte membrane C is finally obtained.
8. The solid electrolyte membrane for lithium ion battery prepared by the method for preparing the solid electrolyte membrane for lithium ion battery according to claim 7 is characterized by comprising continuous phase polyvinylidene fluoride (PVDF), reinforced phase pre-lithiated polyphenylene sulfide (PPS), lithium salt and organic solvent, wherein the weight percentage of PVDF is 40% -50%, the weight percentage of pre-lithiated PPS is 10% -20%, the weight percentage of lithium salt is 20-40%, the weight percentage of organic solvent is 5-15%, and the organic solvent is one or more of N, N-dimethylformamide, tetrahydrofuran and N-methylpyrrolidone (NMP).
9. The lithium ion battery polymer solid electrolyte membrane of claim 8, wherein the crystallinity of the continuous phase polyvinylidene fluoride (PVDF) is <72%; the linear crystallization area of the polyphenylene sulfide is more than 90%.
10. The use of the solid electrolyte membrane according to claim 9 for the preparation of a cell, wherein a metallic lithium negative lithium ion battery or a non-negative lithium ion battery is fabricated, placed between the positive electrode and the negative electrode.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6413676B1 (en) * | 1999-06-28 | 2002-07-02 | Lithium Power Technologies, Inc. | Lithium ion polymer electrolytes |
| CN111342121A (en) * | 2020-02-10 | 2020-06-26 | 江苏大学 | Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof |
| CN111864272A (en) * | 2020-06-09 | 2020-10-30 | 江苏大学 | High-safety volume energy density quasi-solid lithium ion battery and manufacturing method thereof |
| CN112290081A (en) * | 2020-09-22 | 2021-01-29 | 江苏大学 | Manufacturing method of high-energy-density quasi-solid sodium ion battery |
| CN112898569A (en) * | 2021-01-29 | 2021-06-04 | 江苏大学 | Surface functionalized polyphenylene sulfide, solid-liquid dual-phase electrolyte and preparation method thereof |
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- 2023-01-16 CN CN202310062556.2A patent/CN116031479B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6413676B1 (en) * | 1999-06-28 | 2002-07-02 | Lithium Power Technologies, Inc. | Lithium ion polymer electrolytes |
| CN111342121A (en) * | 2020-02-10 | 2020-06-26 | 江苏大学 | Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof |
| CN111864272A (en) * | 2020-06-09 | 2020-10-30 | 江苏大学 | High-safety volume energy density quasi-solid lithium ion battery and manufacturing method thereof |
| CN112290081A (en) * | 2020-09-22 | 2021-01-29 | 江苏大学 | Manufacturing method of high-energy-density quasi-solid sodium ion battery |
| CN112898569A (en) * | 2021-01-29 | 2021-06-04 | 江苏大学 | Surface functionalized polyphenylene sulfide, solid-liquid dual-phase electrolyte and preparation method thereof |
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