CN115719859A - Preparation method of solid-state battery - Google Patents

Preparation method of solid-state battery Download PDF

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CN115719859A
CN115719859A CN202211520727.3A CN202211520727A CN115719859A CN 115719859 A CN115719859 A CN 115719859A CN 202211520727 A CN202211520727 A CN 202211520727A CN 115719859 A CN115719859 A CN 115719859A
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solid
lithium
ion conductor
state battery
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潘燕群
马子朋
孟宪伟
胡波剑
陈玉莲
苏敏
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Wanxiang A123 Systems Asia Co Ltd
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The application discloses a preparation method of a solid-state battery, which specifically comprises the following steps: the method comprises the following steps: uniformly dispersing a polymer precursor, lithium salt and an initiator in a solvent to obtain a mixed solution; step two: assembling a positive plate, a negative plate and a diaphragm into a battery unit, injecting the mixed solution into the battery unit, and sealing the battery unit after the mixed solution is sufficiently soaked; step three: and carrying out formation on the battery unit in a high-temperature pressurized environment, carrying out in-situ polymerization reaction on the polymer precursor, and obtaining the solid battery after the formation is finished. The preparation method of the solid-state battery synchronously improves the interface compatibility between the electrolyte membrane and the electrode by high-temperature formation and in-situ polymerization, reduces the process steps, further shortens the production period of the battery and effectively improves the production efficiency.

Description

Preparation method of solid-state battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a solid-state battery.
Background
With the application of lithium ion batteries in the fields of large-scale power and energy storage such as electric vehicles and smart power grids, higher requirements are put forward on the energy density and safety of the batteries, and the research and development of solid electrolytes are increasingly active. Compared with the traditional liquid lithium ion battery, the solid lithium battery has obvious advantages in the aspects of safety, energy density, assembly process and the like.
Solid electrolytes, which are an important component of solid batteries, are a key issue in the development of solid battery technology. The solid electrolyte mainly comprises an inorganic solid electrolyte (including an oxide solid electrolyte and a sulfide solid electrolyte) and an organic polymer electrolyte, and although the oxide solid electrolyte has excellent stability, the oxide solid electrolyte has the problems of poor conductivity at normal temperature, high processing difficulty, high powder cost and poor contact between the electrolyte and a pole piece; the sulfide solid electrolyte has good ionic conductivity, mechanical strength and flexibility at room temperature, but has poor oxidation stability, poor compatibility with a positive electrode material and strict environmental requirements, and is easy to react with air and water to produce toxic hydrogen sulfide gas; the polymer electrolyte has light weight, good flexibility and low interface resistance, but has low room-temperature ionic conductivity and needs to be used at high temperature.
At present, methods such as in-situ polymerization of electrolyte and the like are generally adopted to improve the interface action between the electrolyte and the pole piece. In-situ polymerization generally requires thermal or photo-initiation, and the prior art generally adds a high temperature treatment or a light irradiation process to the cell before formation of the cell to achieve in-situ polymerization. However, the high temperature treatment generally requires a long time, which prolongs the production cycle of the battery and reduces the production efficiency, and the light irradiation efficiency is high but requires additional equipment.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of the solid-state battery, which synchronously carries out high-temperature formation and in-situ polymerization, improves the interface compatibility between an electrolyte membrane and an electrode, reduces the process steps, further shortens the production period of the battery and effectively improves the production efficiency.
The technical scheme adopted by the invention is as follows: the invention provides a preparation method of a solid-state battery, which specifically comprises the following steps:
the method comprises the following steps: uniformly dispersing a polymer precursor, lithium salt and an initiator in a solvent to obtain a mixed solution;
step two: assembling the positive plate, the negative plate and the diaphragm into a battery unit, injecting the mixed solution into the battery unit, and sealing the battery unit after the mixed solution is sufficiently soaked;
step three: and (3) performing formation on the battery unit in a high-temperature pressurizing environment, performing in-situ polymerization reaction on the polymer precursor, and obtaining the solid battery after the formation is completed.
The method adopts a high-temperature and high-pressure environment in the formation process, so that the polymer precursor can undergo in-situ polymerization reaction in the formation step, namely the traditional formation step and the in-situ polymerization step are simplified into one step, the process steps are simplified on the basis of ensuring the compatibility of a solid-solid interface, and the production efficiency is improved.
Optionally, in the third step, the high temperature is 45-90 deg.C, the high pressure is 0.2-1MPa, and the formation condition is charging at 0.1-1 deg.C for 2-8h. The in-situ polymerization reaction of the polymer precursor can be promoted under the high-temperature condition. The high voltage can make the contact of pole piece and electrolyte diaphragm more inseparable, and interface impedance is littleer, more does benefit to ion transmission. Preferably, the high temperature range is 60-85 ℃, the pressure is 0.5-0.8MPa, the formation condition is 0.2-0.5C charging for 4-6h, the ion transmission efficiency is higher, and the in-situ polymerization reaction is more favorably generated.
Optionally, in the first step, the mass percent of the polymer precursor is 40-90%, the mass percent of the lithium salt is 1-30%, and the mass percent of the initiator is 1-30%; the addition of solvent is 20-100% based on 100% solids content, allowing the polymer precursor to undergo full in situ polymerization. Preferably, the mass percent of the polymer precursor is 50-70%, the mass percent of the lithium salt is 10-20%, the mass percent of the initiator is 5-10%, and the addition amount of the solvent is 30-50% in terms of 100% of solid content.
Optionally, the polymer precursor is selected from any one or more of methyl methacrylate, vinyl acetate, acrylonitrile, vinylidene fluoride, vinyl sulfite, and polyethylene glycol diacrylate.
Optionally, the initiator is selected from any one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, diisobutyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
Optionally, the solvent is any one or combination of ethylene carbonate, vinylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate.
Optionally, the lithium salt is selected from any one or a mixture of more of lithium hexafluorophosphate, lithium perchlorate, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethylsulfonate, lithium bistrifluoromethylsulfonyl imide and lithium bistrifluorosulfonyl imide. The ionic conductivity of the gel polymer electrolyte is much smaller than that of a liquid electrolyte, and particularly under normal temperature conditions, the main factor determining the ionic conductivity at this time is the type and concentration of the lithium salt. Preferably, the lithium salt is selected from any one or more of lithium difluoro (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonyl) imide.
Optionally, the positive electrode layer active material is lithium cobaltate, lithium manganate, lithium iron phosphate, ternary lithium [ lithium nickel cobalt manganese oxide (Li (NiCoMn) O) 2 )]One of (1); the active material of the negative electrode layer is one of graphite, silicon carbon and silicon oxygen.
Optionally, the separator includes a base film and an inorganic fast ion conductor coating layer disposed on the front and/or back side of the base film. Specifically, the coating mode is any one of single-side coating, double-side coating, mixed coating with ceramic and one-side ceramic-fast ion conductor.
Optionally, the inorganic fast ion conductor in the inorganic fast ion conductor coating is selected from LATP (lithium aluminum titanium phosphate, li) 1+ x Al x Ti 2-x (PO 4 ) 3 )、LAGP(Li 1+x Al x Ge 2-x (PO 4 ) 3 Any one or more of LLZO (lithium lanthanum zirconium oxygen) and LLTO (lithium lanthanum titanate). The inorganic fast ion conductor has good ion conducting capacity, lithium ions in the ceramic coating membrane can be only transmitted through the tortuous aperture, and the lithium ions in the inorganic fast ion conductor coating membrane can be directly and quickly transmitted through the fast ion conductor, so that the transmission path is shortened, and the ionic conductivity is improved.
Optionally, the base film is any one of a polyethylene film, a polypropylene film, a polyimide film, and a cellulose film.
Alternatively, the thickness of the inorganic fast ion conductor coating is 1-5 μm, too thin a coating is susceptible to missing coating and undesirable effects, too thick a coating affects energy density and is costly.
The invention has the beneficial effects that: the method adopts a high-temperature and high-pressure environment in the formation process, so that the polymer precursor can be subjected to in-situ polymerization reaction in the formation step, namely the traditional formation step and the in-situ polymerization step are simplified into one step, the process steps are simplified on the basis of ensuring the compatibility of a solid-solid interface, and the production efficiency is improved.
The diaphragm of the invention is coated with the inorganic fast ion conductor coating, and the inorganic fast ion conductor with good ion conducting capability is adopted, compared with the ceramic coated diaphragm in which lithium ions can only be transmitted through the tortuous aperture, the lithium ions in the inorganic fast ion conductor coated film can be directly and fast transmitted through the fast ion conductor, thereby shortening the transmission path and improving the ionic conductivity.
Drawings
Figure 1 is a graph of the EIS of a plugged cell of example 1, example 11, comparative example 3.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. All percentage units are mass percentages unless otherwise specified.
Example 1
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, according to the mass percentage, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film with one side coated with an inorganic fast ion conductor coating containing LLZO as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 60 deg.c and 0.5MPa to form solid cell, and in-situ polymerizing and curing in the presence of hard solid matter in the air bag.
Figure BDA0003969340050000041
Example 2
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, by mass percent, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film with one side coated with an inorganic fast ion conductor coating containing LLZO as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 60 deg.c and 0.1MPa to form the solid cell with in-situ polymerized and cured material.
Example 3
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, by mass percent, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LLZO on one surface as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 60 deg.c and 0.8MPa to form the solid cell, and in-situ polymerizing and curing.
Example 4
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, by mass percent, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LLZO on one surface as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 45 deg.c and 0.5MPa to form the solid cell with in-situ polymerized and cured material.
Example 5
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, according to the mass percentage, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LLZO on one surface as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 90 deg.c and 0.5MPa to form the solid cell, and in-situ polymerizing and curing.
Example 6
Under the protection of argon, acrylonitrile, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, according to the mass percentage, the acrylonitrile accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LLZO on one surface as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 60 deg.c and 0.5MPa to form solid cell, and in-situ polymerizing and curing in the presence of hard solid matter in the air bag.
Figure BDA0003969340050000061
Example 7
Under the protection of argon, vinylidene fluoride, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, according to the mass percentage, the vinylidene fluoride accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LLZO on one surface as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 60 deg.c and 0.5MPa to form solid cell, and in-situ polymerizing and curing in the presence of hard solid matter in the air bag.
Figure BDA0003969340050000062
Example 8
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, according to the mass percentage, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film with one side coated with an inorganic fast ion conductor coating containing LLZO as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 2 mu m. Hot pressing at 60 deg.c and 0.5MPa to form the solid cell with in-situ polymerized and cured material.
Example 9
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, by mass percent, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LLZO on two sides as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 2 mu m. Hot pressing at 60 deg.c and 0.5MPa to form the solid cell with in-situ polymerized and cured material.
Example 10
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, by mass percent, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
The mixed solution is injected into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LATP on one surface as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 60 deg.c and 0.5MPa to form the solid cell with in-situ polymerized and cured material.
Example 11
Under the protection of argon, methyl methacrylate, lithium difluoroborate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, by mass percent, the methyl methacrylate accounts for 60 percent, the lithium difluoro-oxalato-borate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LLZO on one surface as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 60 deg.c and 0.5MPa to form the solid cell with in-situ polymerized and cured material.
Example 12
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate, lithium difluoroborate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, by mass percent, the methyl methacrylate accounts for 60%, the lithium hexafluorophosphate accounts for 18%, the lithium difluoroborate accounts for 20%, the azobisisobutyronitrile accounts for 2%, and the solvent accounts for 30%.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LLZO on one surface as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. And (3) carrying out high-temperature pressurization formation at the temperature of 60 ℃ and under the pressure of 0.5MPa to obtain the in-situ polymerization cured solid-state battery.
Example 13
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, according to the mass percentage, the methyl methacrylate accounts for 78 percent, the lithium hexafluorophosphate accounts for 20 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film coated with an inorganic fast ion conductor coating containing LLZO on one surface as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. Hot pressing at 60 deg.c and 0.5MPa to form the solid cell with in-situ polymerized and cured material.
Comparative example 1
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, according to the mass percentage, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery unit which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film as a diaphragm, and carrying out hot pressing at 60 ℃ under the condition of 0.5MPa until solid hard substances appear in an air bag, thus obtaining the solid battery solidified by in-situ polymerization.
Comparative example 2
Under the protection of argon, methyl methacrylate, lithium hexafluorophosphate and azobisisobutyronitrile are added into an EC/DMC (1). Wherein, according to the mass percentage, the methyl methacrylate accounts for 60 percent, the lithium hexafluorophosphate accounts for 38 percent, the azobisisobutyronitrile accounts for 2 percent, and the solvent accounts for 30 percent.
And injecting the mixed solution into a battery cell which takes ternary lithium as a positive electrode, graphite as a negative electrode and a polyethylene film with one side coated with an inorganic fast ion conductor coating containing LLZO as a diaphragm, wherein the thickness of the inorganic fast ion conductor coating is 3 mu m. The reaction solution was reacted at 25 ℃ under 0.5MPa for 5 hours.
Comparative example 3
Under the protection of argon, lithium hexafluorophosphate was added to an EC/DMC (1) mixed solvent to prepare a uniform solution with a mass fraction of 38%.
And injecting the solution into a battery unit which takes ternary lithium as a positive electrode, takes graphite as a negative electrode and takes an inorganic fast ion conductor coating layer containing LLZO and a 3-micron polyethylene film coated on one surface as a diaphragm, and pressurizing and forming at normal temperature under the condition of 0.5MPa to obtain the liquid lithium ion battery.
Table 1 ionic conductivity test results
Figure BDA0003969340050000091
As can be seen from the ion conductivity data of each example and comparative example in table 1, examples 1, 2 and 3 are different in the formation pressure, and the higher the formation pressure, the higher the ion conductivity, because the pressure makes the contact between the electrode sheet and the electrolyte membrane closer, the lower the interface impedance, and the better the ion transmission.
Examples 1, 4, 5 and 2 are different in temperature at formation, example 1 is at 60 ℃, example 4 is at 45 ℃, example 5 is at 90 ℃ and comparative example 2 is at 25 ℃, and the ionic conductivity is not greatly affected when the temperature reaches a certain degree, except that in-situ polymerization does not occur when the temperature is low.
The difference between the embodiments 1, 6 and 7 is that the types of the available polymer precursors have little influence on the ionic conductivity, because the polymer precursors are different.
Examples 1, 11 and 12 differ in the lithium salt, with lithium hexafluorophosphate being used in example 1, lithium difluorooxalato borate being used in example 11, lithium hexafluorophosphate and lithium difluorooxalato borate being used in example 12. Examples 1, 13 and comparative example 3 differ in the amount of methyl methacrylate used, 60% for example 1, 78% for example 13 and no polymer precursor and no initiator for comparative example 3. Referring to the EIS spectra of the blocking batteries of example 1, example 11 and comparative example 3 in fig. 1 in combination, the in-situ polymerized ionic conductivity is slightly smaller compared with the liquid electrolyte, and as the addition amount of the polymer precursor is larger, the polymer generated after polymerization is larger, but the ionic conductivity is lower due to the relatively lower addition amount of the lithium salt; the in-situ polymerization ionic conductivity is mainly determined by the type and concentration of the lithium salt.
The difference between example 1 and example 8 is that the inorganic fast ion conductor coating has different coating thickness, the coating thickness is large, the ion conductivity is relatively large, but the synergy is not obvious. The difference between example 8 and example 9 is that the inorganic fast ion conductor coating in example 8 is single-sided coating, while example 9 is double-sided coating, and the available double-sided coating can increase the ion conductivity, but the synergy is not obvious. The difference between the example 1 and the example 10 is that the kind of the inorganic fast ion conductor is different, the LLZO is used in the example 1, the LATP is used in the example 10, and the influence of the kind of the inorganic fast ion conductor on the ion conductivity is limited. Example 1 is different from comparative example 1 in that comparative example 1 is not coated with an inorganic fast ion conductor coating, and the application of the available inorganic fast ion conductor coating can improve the ion conductivity to some extent.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings can be directly or indirectly applied to other related technical fields and are included in the scope of the present invention.

Claims (10)

1. The preparation method of the solid-state battery is characterized by comprising the following steps:
the method comprises the following steps: uniformly dispersing a polymer precursor, lithium salt and an initiator in a solvent to obtain a mixed solution;
step two: assembling a positive plate, a negative plate and a diaphragm into a battery unit, injecting the mixed solution into the battery unit, and sealing the battery unit after the mixed solution is sufficiently soaked;
step three: and carrying out formation on the battery unit in a high-temperature pressurized environment, carrying out in-situ polymerization reaction on the polymer precursor, and obtaining the solid battery after the formation is finished.
2. The method for manufacturing a solid-state battery according to claim 1, wherein in the third step, the temperature of the high temperature is in a range of 45 to 90 ℃, the high pressure is in a range of 0.2 to 1MPa, and the formation conditions are 0.1 to 1C for 2 to 8 hours.
3. The method for manufacturing a solid-state battery according to claim 2, wherein in the first step, the mass percentage of the polymer precursor is 40 to 90%, the mass percentage of the lithium salt is 1 to 30%, and the mass percentage of the initiator is 1 to 30%;
the addition amount of the solvent is 20-100% based on 100% of solid content.
4. The method for producing a solid-state battery according to claim 3, wherein the polymer precursor is selected from any one or more of methyl methacrylate, vinyl acetate, acrylonitrile, vinylidene fluoride, vinyl sulfite, and polyethylene glycol diacrylate.
5. The method for producing a solid-state battery according to claim 3, wherein the initiator is selected from any one or a mixture of two or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, diisobutyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
6. The method of manufacturing a solid-state battery according to claim 3, wherein the lithium salt is selected from any one or a mixture of more of lithium hexafluorophosphate, lithium perchlorate, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonylimide and lithium difluorosulfonylimide.
7. The method for manufacturing a solid-state battery according to any one of claims 1 to 6, wherein the separator comprises a base film and an inorganic fast ion conductor coating layer, and the inorganic fast ion conductor coating layer is disposed on the front and/or back surface of the base film.
8. The method of claim 7, wherein the inorganic fast ion conductor in the inorganic fast ion conductor coating is selected from a mixture of any one or more of LATP, LAGP, LLZO, and LLTO.
9. The method of manufacturing a solid-state battery according to claim 8, wherein the base film is any one of a polyethylene film, a polypropylene film, a polyimide film, and a cellulose film.
10. The method of manufacturing a solid-state battery according to claim 9, wherein the inorganic fast ion conductor coating layer has a thickness of 1 to 5 μm.
CN202211520727.3A 2022-11-29 2022-11-29 Preparation method of solid-state battery Pending CN115719859A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117747937A (en) * 2024-02-06 2024-03-22 河南新太行电源股份有限公司 Quasi-solid state battery and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117747937A (en) * 2024-02-06 2024-03-22 河南新太行电源股份有限公司 Quasi-solid state battery and preparation method thereof

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