CN118017020A - Preparation method of high-voltage-resistant solid polymer lithium metal battery - Google Patents
Preparation method of high-voltage-resistant solid polymer lithium metal battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 101
- 229920000642 polymer Polymers 0.000 title claims abstract description 77
- 239000007787 solid Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 37
- 239000011241 protective layer Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 27
- 239000002033 PVDF binder Substances 0.000 claims description 22
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 19
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- -1 Polysiloxane Polymers 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- 239000004632 polycaprolactone Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 claims description 4
- 229940053009 ethyl cyanoacrylate Drugs 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 3
- 229920002313 fluoropolymer Polymers 0.000 claims description 3
- 239000004811 fluoropolymer Substances 0.000 claims description 3
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 claims description 2
- 229910010848 Li6PS5Cl Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229920002721 polycyanoacrylate Polymers 0.000 claims description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
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- 238000004090 dissolution Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
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- 229920000307 polymer substrate Polymers 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
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Abstract
The invention belongs to the field of lithium metal batteries, and discloses a preparation method of a high-voltage-resistant solid polymer lithium metal battery. The preparation method of the invention comprises the steps of respectively forming a high-voltage resistant polymer electrolyte and a polymer lithium metal protective layer on a high-voltage positive electrode and a lithium metal negative electrode in situ. The high-voltage resistant polymer electrolyte on the high-voltage positive electrode can ensure that the battery stably runs under a high-potential working condition; the polymer protective layer on the lithium metal electrode can ensure that the battery is prevented from being damaged by oxygen, water and other substances possibly reacting with lithium metal in the air assembly process, and simultaneously can ensure that the battery is prevented from being damaged by organic substances from electrolyte or electrolyte in the operation process of the battery.
Description
Technical Field
The invention relates to the field of lithium metal batteries, in particular to a preparation method of a high-voltage-resistant solid polymer lithium metal battery.
Background
The current chemical property of lithium metal is limited, the assembly process of the lithium metal battery is required to be carried out in an oxygen-free and water-free environment, and the high environmental requirement greatly improves the preparation cost of the battery. The polymer protective layer on the lithium metal electrode can ensure that the battery is protected from oxygen, water and other substances possibly reacting with lithium metal in the process of assembling in the air, but the high-voltage polymer solid lithium metal battery has some problems, and on one hand, a polymer electrolyte capable of bearing high voltage usually remains a part of organic solvents during preparation, and the organic solvents promote rapid conduction of lithium ions in the polymer, but on the other hand, the problem of damaging the battery health due to side reactions with a lithium metal cathode is faced. Secondly, the conventional polymer electrolyte can not damage lithium metal when contacting with the lithium metal, but has the disadvantage of being difficult to bear the stable operation of the battery at higher voltage.
There is currently no good solution to the first problem described above. For the second problem, the main solutions at present are two methods, namely, strictly controlling the content of the metal-unstable chemical solvent in the high-pressure resistant polymer electrolyte or limiting the diffusion of the chemical solvent by special means; and secondly, the common polymer electrolyte is modified, and although the method improves the high-pressure resistance of the electrolyte to a certain extent, the process is complex and high in cost, stays in a laboratory stage, and is difficult to produce in a large scale. Therefore, a method is needed to solve the above problems at the same time.
Disclosure of Invention
The invention aims to overcome the defects of the background technology, effectively solves the problems by using a high-voltage resistant polymer electrolyte and a lithium metal stable polymer, and provides a preparation method of a high-voltage resistant solid polymer lithium metal battery. According to the preparation method, the polymer electrolyte stable to lithium metal is prepared on the surface of the lithium metal in situ through a simple physical method, so that a lithium metal protective layer is formed, oxygen and water in air can be isolated from corrosion of the lithium metal during assembly, meanwhile, shuttling of lithium ions can be ensured during operation of the battery, corrosion of chemical reagents harmful to the lithium metal from the electrolyte to the lithium metal is prevented, and the solid polymer electrolyte capable of bearing high voltage, prepared on a high-voltage positive electrode, ensures stable operation of the battery under high voltage.
In order to achieve the purpose of the invention, the preparation method of the high-voltage resistant solid polymer lithium metal battery comprises the following steps:
(1) Dissolving a high-voltage resistant polymer in an organic solvent to prepare a polymer solution with a certain concentration, adding lithium salt and inorganic nano particles for promoting lithium ion conduction into the solution, and uniformly stirring to form a solid polymer electrolyte solution;
(2) Dissolving a lithium metal protective layer polymer in an organic solvent to prepare a polymer solution with a certain concentration, adding lithium salt for promoting lithium ion conduction into the solution, and uniformly stirring to form a negative electrode protective layer solution;
(3) The solid polymer electrolyte solution is directly coated on the positive electrode and dried to form the solid polymer electrolyte, so that the positive electrode with the high-pressure-resistant polymer electrolyte is obtained, and the thickness of the positive electrode is adjusted according to actual needs, and can be realized by coating the thickness;
(4) Directly coating the negative electrode protective layer solution on lithium metal cut into a required size, and drying to form a lithium metal protective layer to obtain a lithium metal negative electrode with a protective layer, wherein the thickness of the lithium metal negative electrode is adjusted according to actual needs;
(5) The positive electrode with the high-voltage resistant polymer electrolyte and the lithium metal negative electrode with the protective layer obtained in the above manner are assembled in a conventional manner, and the environment during the battery assembly is not limited because the protective layer is arranged on the surface of the lithium metal.
Further, in some embodiments of the present invention, the high voltage resistant polymer in step (1) is one or more of a fluoropolymer, a cyano-containing polymer, polycaprolactone (PCL), polyoxalate (POE); preferably, the fluoropolymer is polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF); preferably, the cyano-containing polymer is polycyanoacrylate, ethyl Cyanoacrylate (ECA); more preferably, the high voltage resistant polymer in step (1) is polyvinylidene fluoride (PVDF).
Further, in some embodiments of the present invention, the lithium metal protective layer polymer in step (2) is one or more of chlorine-containing polymer, ether polymer, polysiloxane (PS); preferably, the chlorine-containing polymer is one or more of polyvinyl chloride (PVC), polyvinylidene chloride (PVDC); preferably, the ether polymer is one or more of polyethylene oxide (PEO), ethylene glycol methyl ether methacrylate (PEGMA), and polydioxolane (P-DOL); more preferably, the lithium metal protective layer polymer in step (2) is polyvinylidene chloride (PVDC).
Further, in some embodiments of the present invention, the lithium salt in step (1) and step (2) is one or more of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide), lithium bis (trifluoromethylsulfonimide).
Further, in some embodiments of the invention, the inorganic nanoparticles in step (1) are one or more of silica, zirconia, titania 、Li7La3Zr2O12、Li6.4La3Zr1.4Ta0.6O12、Li10GeP2S12、Li6PS5Cl.
Further, in some embodiments of the present invention, the mass ratio of the high voltage resistant polymer, lithium salt, and inorganic nanoparticles in the step (1) is 40 to 70:5-40:5-30.
Different polymers in the preparation method of the invention are dissolved by corresponding solvents, and the solvents which are preferable for polyvinylidene fluoride (PVDF) in the step (1) of the preparation method are N, N-Dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc) and can be selected by a person skilled in the art according to physical property information; preferred solvents for polyvinylidene chloride (PVDC) preferred for step (2) of the above preparation process are Tetrahydrofuran (THF), dichloromethane (DCM).
Further, in some embodiments of the present invention, the organic solvent used in step (1) is a poor solvent for the lithium metal protective layer polymer of step (2), and the organic solvent used in step (2) is a poor solvent for the high voltage resistant polymer of step (1).
Further, in some embodiments of the present invention, the solvent content of the solid polymer electrolyte solution of step (1) is 5 to 10% to promote lithium ion conduction.
Further, in some embodiments of the present invention, the solvent content in the negative electrode protection layer solution of step (2) is 5 to 10% to promote lithium ion conduction.
Further, in some embodiments of the present invention, the preparation of the lithium metal protective layer in step (4) is performed in a glove box filled with an inert gas, and the values of water and oxygen in the glove box should be less than 0.1ppm.
Further, in some embodiments of the present invention, the step (5) is performed by adding an electrolyte between the high pressure resistant polymer and the lithium metal protective layer polymer for wetting during assembly.
Compared with the prior art, the invention has the following advantages:
(1) The use of a high voltage stable polymer substrate at the positive electrode/electrolyte interface in the present invention can better match the high voltage positive electrode.
(2) The lithium metal stabilizing polymer is used at the lithium metal anode/electrolyte interface, so that the corrosion of the lithium metal to moist air and organic solvents can be effectively prevented, and the chemical stabilization of the lithium metal electrode is realized. Therefore, the composite electrolyte has a wide electrochemical stability window and excellent positive electrode interface stability.
(3) In practical application, the technology of the invention can be used as a solid electrolyte of a lithium metal battery with high energy density, and can simultaneously meet the requirement of assembling the lithium metal battery in air, and the prepared high-voltage solid lithium metal battery has high initial discharge specific capacity and reliable cycle and multiplying power performance.
Drawings
FIG. 1 is a schematic diagram showing the performance of the battery obtained in example 1 of the present invention in long-term charge-discharge cycles;
FIG. 2 is a schematic diagram showing the performance of the battery obtained in example 2 of the present invention in long-term charge-discharge cycles;
FIG. 3 is a schematic diagram showing the performance of the battery according to comparative example 1 of the present invention in a long-time charge-discharge cycle;
Fig. 4 is a schematic diagram showing the performance of the battery obtained in comparative example 2 according to the present invention in a long-time charge-discharge cycle.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is intended to be illustrative of the invention and not restrictive.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
The preparation method of the high-voltage-resistant solid polymer lithium metal battery comprises the following steps:
1. Polyvinylidene fluoride (PVDF), lithium bis-difluorosulfonimide (LiTFSI), li 6.4La3Zr1.4Ta0.6O12 according to 0.6g:0.1g:0.3g of the solution is added into 15mL of N, N-Dimethylformamide (DMF) organic solvent and stirred overnight for dissolution, so as to obtain PVDF polymer electrolyte solution;
2. Polyvinylidene chloride (PVDC), lithium bis-difluorosulfonimide (LiTFSI) was mixed according to 1.0g: adding 0.4g of the PVDC polymer solution into 15mL of Tetrahydrofuran (THF) organic solvent according to the mass ratio, stirring for one day and night for dissolution, and obtaining PVDC polymer solution;
3. 100 μl of the PVDF polymer electrolyte solution obtained in step 1 was dripped onto the NCM811 positive electrode with a diameter of 12mm, and then subjected to volatilization for 24 hours to obtain a polymer electrolyte;
4. In a glove box with water and oxygen concentration less than 0.1ppm, 175 mu l of PVDC polymer solution obtained in the step 2 is dripped on a lithium metal sheet with the diameter of 18mm, and a lithium metal protection layer is obtained after 12h of volatilization;
5. After the above steps are completed, the button cell can be assembled in air according to conventional steps. It should be noted that 15. Mu.l of electrolyte was added between PVDC polymer and PVDF polymer for wetting at the time of assembly.
6. After the battery was left to stand for 12 hours, the battery was subjected to a charge-discharge curve at a rate of 0.5C.
Example 2
The preparation method of the high-voltage-resistant solid polymer lithium metal battery comprises the following steps:
1. Polyvinylidene fluoride (PVDF), lithium bis-difluorosulfonimide (LiTFSI), li 6.4La3Zr1.4Ta0.6O12, at 0.8g:0.15g:0.6g of the PVDF polymer electrolyte solution is added into 20mL of N, N-Dimethylformamide (DMF) organic solvent according to the mass ratio, and stirred overnight for dissolution;
2. Polyvinylidene chloride (PVDC), lithium bis-difluorosulfonimide (LiTFSI) was mixed according to 1.5g: adding 0.5g of the PVDC polymer solution into 20mL of Tetrahydrofuran (THF) organic solvent according to the mass ratio, stirring for one day and night for dissolution, and obtaining PVDC polymer solution;
3. dropping 80 mu l of PVDF polymer electrolyte solution obtained in the step 1 on an LCO positive electrode with the diameter of 12mm, and volatilizing for 24 hours to obtain polymer electrolyte;
4. in a glove box with water and oxygen concentration less than 0.1ppm, 155 mu l of PVDC polymer solution obtained in the step 2 is dripped on a lithium metal sheet with the diameter of 18mm, and a lithium metal protection layer is obtained after 12h of volatilization;
5. After the above steps are completed, the button cell can be assembled in air according to conventional steps. It should be noted that 15. Mu.l of electrolyte was added between PVDC polymer and PVDF polymer for wetting at the time of assembly.
6. After the battery was left to stand for 12 hours, the battery was subjected to a charge-discharge curve at a rate of 0.1C.
Example 3
The preparation method of the high-voltage-resistant solid polymer lithium metal battery comprises the following steps:
1. polycaprolactone (PCL) and lithium hexafluorophosphate (LiPF 6）、Li7La3Zr2O12, mass ratio of 0.3g:0.04g:0.14 g) are added into 10mL of N, N-Dimethylformamide (DMF) organic solvent, and stirred overnight for dissolution, so as to obtain PCL polymer electrolyte solution;
2. ethylene Vinyl Acetate (EVA), lithium hexafluorophosphate (LiPF 6) was used in an amount of 0.8g: adding 0.23g of the EVA polymer into 10mL of Tetrahydrofuran (THF) organic solvent according to the mass ratio, stirring for one day and night for dissolution to obtain EVA polymer solution;
3. 100 μl of the PCL polymer electrolyte solution obtained in step 1 was dripped on the NCM523 positive electrode with a diameter of 12mm, and then subjected to volatilization for 24 hours to obtain a polymer electrolyte;
4. Dripping 125 mu l of the EVA polymer solution obtained in the step 2 on a lithium metal sheet with the diameter of 18mm in a glove box with the water and oxygen concentration of less than 0.1ppm, and volatilizing for 12 hours to obtain a lithium metal protective layer;
5. After the above steps are completed, the button cell can be assembled in air according to conventional steps. It should be noted that 15. Mu.l of electrolyte is added between the PCL polymer and the EVA polymer for wetting during assembly;
6. After the battery was left to stand for 12 hours, the battery was subjected to a charge-discharge curve at a rate of 0.3C.
Comparative example 1
A preparation method of a lithium metal battery comprises the following steps:
1. Polyvinylidene fluoride (PVDF), lithium bis-difluorosulfonimide (LiTFSI), li 6.4La3Zr1.4Ta0.6O12, at 0.6g:0.1g:0.3g of the solution is added into 15mL of N, N-Dimethylformamide (DMF) organic solvent and stirred overnight for dissolution, so as to obtain PVDF polymer electrolyte solution;
2. 100 μl of the PVDF polymer electrolyte solution obtained in step 1 was dripped onto the NCM811 positive electrode with a diameter of 12mm, and then subjected to volatilization for 24 hours to obtain a polymer electrolyte;
3. Then, in a glove box with the water and oxygen concentrations smaller than 0.1ppm, assembling a lithium metal battery by taking lithium metal as a negative electrode; it should be noted that 15 μl of electrolyte was added between the electrolyte and the lithium metal for wetting;
4. after the battery was left to stand for 12 hours, the battery was subjected to a charge-discharge curve at a rate of 0.5C.
Comparative example 2
A preparation method of a lithium metal battery comprises the following steps:
1. Polyvinylidene chloride (PVDC), lithium bis-difluorosulfonimide (LiTFSI) was mixed according to 1.0g: adding 0.4g of the PVDC polymer electrolyte solution into 10mL of Tetrahydrofuran (THF) organic solvent according to the mass ratio, stirring for one day and night for dissolution, and obtaining PVDC polymer electrolyte solution;
2. 200 μl of the PVDC polymer electrolyte solution obtained in step 1 was dripped on NCM811 with a diameter of 12mm, and the PVDC polymer electrolyte was obtained by volatilization for 12 hours;
3. Then, in a glove box with the water and oxygen concentrations smaller than 0.1ppm, assembling a lithium metal battery by taking lithium metal as a negative electrode; it should be noted that 15 μl of electrolyte was added between the electrolyte and the lithium metal for wetting;
4. after the battery was left to stand for 12 hours, the battery was subjected to a charge-discharge curve at a rate of 0.5C.
The results of performance tests of the batteries obtained in the above examples and comparative examples are shown below.
| Test item | Charging voltage | Charge-discharge multiplying power | Specific capacity after 100 cycles (mAh/g) | Capacity retention after 100 cycles (%) |
| Example 1 | 4.3 | 0.5C | 133.1 | 94.7 |
| Example 2 | 4.3 | 0.1C | 117.7 | 86.3 |
| Example 3 | 4.3 | 0.3C | 141.3 | 91.2 |
| Comparative example 1 | 4.3 | 0.5C | 74.1 | 80.2 |
| Comparative example 2 | 4.3 | 0.5C | 0 | 0 |
In example 1, a battery using NCM811 as a high-voltage positive electrode and lithium metal as a negative electrode was subjected to a long-time charge-discharge cycle at a high current density, and as shown in fig. 1, the battery had a stable discharge capacity and coulombic efficiency, and the capacity retention rate reached 84.2% when the battery was cycled for 200 cycles at a 0.5C magnification, and the reversible capacity was still greater than 70% after extending to 300 cycles, and the average coulombic efficiency was greater than 98.5% throughout the cycle, and the battery still had almost coincident charge-discharge curves even after multiple charge-discharge cycles.
In example 2, a battery using LCO as a high-voltage positive electrode and lithium metal as a negative electrode was subjected to long-time charge-discharge cycles at a high current density, and as shown in fig. 2, the battery had a stable discharge capacity and coulombic efficiency, and also had good cycle stability and coulombic efficiency close to 100% at a current density of 0.1C, and a capacity retention rate of 80% or more was still maintained at 150 times of charge-discharge.
As shown in fig. 3, the battery of comparative example 1 using the high-voltage resistant electrolyte alone, in which NCM811 was used as the high-voltage positive electrode and lithium metal was used as the negative electrode, was subjected to charge and discharge cycles at a high current density for a long period of time, and exhibited a low capacity from the beginning.
As shown in fig. 4, comparative example 2 used a common electrolyte alone, and a battery having NCM811 as a high-voltage positive electrode and lithium metal as a negative electrode was subjected to a charge-discharge cycle for a long period of time at a high current density, exhibited a particularly low capacity from the beginning, and the battery had failed within 100 times of charge-discharge.
It will be readily appreciated by those skilled in the art that the foregoing is merely a partial example of the present invention and is not intended to limit the invention, but any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing a high-voltage-resistant solid polymer lithium metal battery, which is characterized by comprising the following steps:
(1) Dissolving a high-voltage resistant polymer in an organic solvent to prepare a polymer solution with a certain concentration, adding lithium salt and inorganic nano particles for promoting lithium ion conduction into the solution, and uniformly stirring to form a solid polymer electrolyte solution;
(2) Dissolving a lithium metal protective layer polymer in an organic solvent to prepare a polymer solution with a certain concentration, adding lithium salt for promoting lithium ion conduction into the solution, and uniformly stirring to form a negative electrode protective layer solution;
(3) The solid polymer electrolyte solution is directly coated on the positive electrode and dried to form the solid polymer electrolyte, so that the positive electrode with the high-pressure-resistant polymer electrolyte is obtained, and the thickness of the positive electrode is adjusted according to actual needs, and can be realized by coating the thickness;
(4) Directly coating the negative electrode protective layer solution on lithium metal cut into a required size, and drying to form a lithium metal protective layer to obtain a lithium metal negative electrode with a protective layer, wherein the thickness of the lithium metal negative electrode is adjusted according to actual needs;
(5) The positive electrode with the high-voltage resistant polymer electrolyte and the lithium metal negative electrode with the protective layer obtained in the above manner are assembled in a conventional manner, and the environment during the battery assembly is not limited because the protective layer is arranged on the surface of the lithium metal.
2. The method for preparing a high voltage resistant solid polymer lithium metal battery according to claim 1, wherein the high voltage resistant polymer in the step (1) is one or more of a fluoropolymer, a cyano-containing polymer, polycaprolactone (PCL), and Polyoxalate (POE); the fluorine-containing polymer is polyvinyl fluoride (PVF) or polyvinylidene fluoride (PVDF); the cyano-containing polymer is polycyanoacrylate and Ethyl Cyanoacrylate (ECA).
3. The method for preparing a lithium metal battery of a high-voltage resistant solid polymer according to claim 1, wherein the lithium metal protective layer polymer in the step (2) is one or more of chlorine-containing polymer, ether polymer and Polysiloxane (PS); the chlorine-containing polymer is one or more of polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC); the ether polymer is one or more of polyethylene oxide (PEO), ethylene glycol methyl ether methacrylate (PEGMA) and polydioxolane (P-DOL).
4. The method for preparing a high-voltage resistant solid polymer lithium metal battery according to claim 1, wherein the lithium salt in the step (1) and the step (2) is one or more of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisdifluorosulfonimide and lithium bistrifluoromethylsulfonimide.
5. The method for preparing a high-voltage resistant solid polymer lithium metal battery according to claim 1, wherein the inorganic nanoparticles in the step (1) are one or more of silica, zirconia and titania 、Li7La3Zr2O12、Li6.4La3Zr1.4Ta0.6O12、Li10GeP2S12、Li6PS5Cl.
6. The method for preparing the high-voltage resistant solid polymer lithium metal battery according to claim 1, wherein the mass ratio of the high-voltage resistant polymer, the lithium salt and the inorganic nano particles in the step (1) is 40-70:5-40:5-30.
7. The method for preparing a lithium metal battery of a high voltage resistant solid polymer according to claim 1, wherein the organic solvent used in the step (1) is a poor solvent for the lithium metal protective layer polymer in the step (2), and the organic solvent used in the step (2) is a poor solvent for the high voltage resistant polymer in the step (1).
8. The method for preparing a high-voltage resistant solid polymer lithium metal battery according to claim 1, wherein the solvent content in the solid polymer electrolyte solution in the step (1) is 5-10% to promote lithium ion conduction.
9. The method for preparing a high-voltage resistant solid polymer lithium metal battery according to claim 1, wherein the solvent content in the negative electrode protection layer solution in the step (2) is 5-10% to promote lithium ion conduction.
10. The method for preparing a high-voltage resistant solid polymer lithium metal battery according to claim 1, wherein the preparation of the lithium metal protective layer in the step (4) is performed in a glove box filled with inert gas, and the values of water and oxygen in the glove box are less than 0.1ppm.
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| US20200303729A1 (en) * | 2016-03-28 | 2020-09-24 | Seven King Energy Co., Ltd. | Composite electrolyte for secondary battery, having multi-layer structure |
| JP2020177890A (en) * | 2019-04-15 | 2020-10-29 | ＡＲＭ Ｔｅｃｈｎｏｌｏｇｉｅｓ株式会社 | Non-aqueous secondary battery |
| CN112366293A (en) * | 2020-11-10 | 2021-02-12 | 广东天劲新能源科技股份有限公司 | Solid metal lithium battery and preparation method thereof |
| CN116169366A (en) * | 2022-12-27 | 2023-05-26 | 力神（青岛）新能源有限公司 | Solid-state lithium battery, preparation method thereof and electric equipment |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200303729A1 (en) * | 2016-03-28 | 2020-09-24 | Seven King Energy Co., Ltd. | Composite electrolyte for secondary battery, having multi-layer structure |
| JP2020177890A (en) * | 2019-04-15 | 2020-10-29 | ＡＲＭ Ｔｅｃｈｎｏｌｏｇｉｅｓ株式会社 | Non-aqueous secondary battery |
| CN112366293A (en) * | 2020-11-10 | 2021-02-12 | 广东天劲新能源科技股份有限公司 | Solid metal lithium battery and preparation method thereof |
| CN116169366A (en) * | 2022-12-27 | 2023-05-26 | 力神（青岛）新能源有限公司 | Solid-state lithium battery, preparation method thereof and electric equipment |
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