CN109786817B - Solid lithium battery, application thereof and method for preparing non-woven fabric reinforced solid electrolyte membrane - Google Patents

Solid lithium battery, application thereof and method for preparing non-woven fabric reinforced solid electrolyte membrane Download PDF

Info

Publication number
CN109786817B
CN109786817B CN201910063972.8A CN201910063972A CN109786817B CN 109786817 B CN109786817 B CN 109786817B CN 201910063972 A CN201910063972 A CN 201910063972A CN 109786817 B CN109786817 B CN 109786817B
Authority
CN
China
Prior art keywords
lithium battery
woven fabric
solid
lithium
binder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910063972.8A
Other languages
Chinese (zh)
Other versions
CN109786817A (en
Inventor
梭楚姆·乔伊库马尔
王磊
吕文彬
黄海强
郑晓醒
周龙捷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Svolt Energy Technology Co Ltd
Original Assignee
Svolt Energy Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Svolt Energy Technology Co Ltd filed Critical Svolt Energy Technology Co Ltd
Priority to CN201910063972.8A priority Critical patent/CN109786817B/en
Publication of CN109786817A publication Critical patent/CN109786817A/en
Application granted granted Critical
Publication of CN109786817B publication Critical patent/CN109786817B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a solid-state lithium battery, application thereof and a method for preparing a non-woven fabric reinforced solid-state electrolyte membrane. The non-woven fabric reinforced solid electrolyte membrane has high mechanical strength and thermal stability, and meanwhile, no anode and cathode short circuit occurs in the assembling and using processes of a solid battery, so that the preparation success rate is high, and in the using process of the battery, the phenomenon that dendrites penetrate through electrodes is remarkably reduced, so that the non-woven fabric reinforced solid electrolyte membrane is very suitable for large-batch industrial production and has remarkable commercial property.

Description

Solid lithium battery, application thereof and method for preparing non-woven fabric reinforced solid electrolyte membrane
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a solid-state lithium battery, application thereof and a method for preparing a non-woven fabric reinforced solid-state electrolyte membrane.
Background
In recent years, vehicles have been widely used to alleviate air pollution and global warming crisis faced by human beings. For the lithium battery adopted by the current vehicle, the technology is the most advanced technology in the industry. However, lithium battery technology has many drawbacks in terms of safety and performance: on one hand, the explosion is easily caused by thermal runaway due to the use of flammable and corrosive liquid electrolyte; on one hand, because of the hidden danger, a large number of battery protection systems are needed, so that the overall energy density of the battery is low; on the one hand, poor cycling performance of the battery can result from the formation of lithium dendrites, chemical degradation of the liquid electrolyte and the electrode surface.
Recently, safer solid-state lithium batteries having high energy density have been developed. Solid state lithium batteries provide a remedy for most of the technical shortcomings of liquid state lithium batteries. Lithium Ion Batteries (LiB) and Fuel Cells (FC) are currently the primary energy sources for vehicular applications. However, the most advanced LiB technology in the industry has problems of imminence, mainly safety and mileage. To address these problems, great efforts have been made to develop solid state lithium batteries for vehicles and other applications. However, mass production and commercialization of solid lithium batteries have not been achieved due to problems such as short circuit during assembly, formation of dendrites during use, inability to produce high yields and low production efficiency while lacking a separator having high mechanical strength, uniform distribution of substances and flexibility. Furthermore, there are still limitations in manufacturing solid state lithium batteries using sulfide solid electrolytes with low overall impedance and high cycle life, and in achieving large sizes with scalable electrodes, variable current collectors.
Therefore, the existing technology for preparing solid lithium batteries needs to be further improved.
Disclosure of Invention
In view of the above, the present invention is directed to a solid lithium battery, and an application thereof and a method for preparing a non-woven fabric reinforced solid electrolyte membrane, so as to solve the problems that the conventional solid lithium battery is prone to short circuit during assembly, to dendrite formation during use, to mass industrial production, and to have no separator with high mechanical strength, uniform material distribution, and flexibility.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a solid state lithium battery, comprising: a non-woven fabric reinforced solid electrolyte membrane, a positive electrode, a negative electrode and a buffer layer.
Further, the non-woven fabric-reinforced solid electrolyte membrane includes: a first solid sulfide electrolyte, a nonwoven fabric, and a first binder.
Further, the positive electrode comprises an aluminum foil and a composite positive electrode, and the composite positive electrode comprises: the composite material comprises a positive electrode active material, a nano coating material, a second solid sulfide electrolyte, a first conductive material and a second adhesive, wherein the nano coating material is coated on the surface of the positive electrode active material.
Further, the negative electrode comprises a current collector and a negative electrode material, wherein the current collector is a copper foil or a nickel foil, and the negative electrode material is lithium or indium or a lithium-indium alloy or a composite negative electrode.
Further, the composite anode includes: a negative active material, a solid electrolyte, a second conductive material, and a third binder.
Further, the tensile strength of the non-woven fabric reinforced solid electrolyte membrane is 100-10000N/cm2And the elongation is 0-50%.
Further, in the nonwoven fabric-reinforced solid electrolyte membrane, the mass ratio of the first solid sulfide electrolyte to the nonwoven fabric, the first binder is 80 to 97: 0.01-20: 3-10.
Further, the non-woven fabric is at least one of a PP-based non-woven fabric, a PE-based non-woven fabric, a PET-based non-woven fabric, a PAN-based non-woven fabric, a PTFE-based non-woven fabric, and a Celgard non-woven fabric.
Further, the gram weight of the non-woven fabric is 1-10g/m2The porosity is 50-95%, the thickness is 10-50 μm, and the tensile strength is 200-4500N/cm2。
Further, the first binder is at least one of an ethylene oxide polymer, a vinyl polymer, a vinylidene fluoride polymer, a styrene polymer, and a butadiene polymer.
Further, the molecular weight of the first binder is 100000-1000000.
Further, the non-woven fabric reinforced solid electrolyte further comprises a first lithium salt, wherein the first lithium salt is selected from LiTFSI, LiFSI and LiN (SO)2CF2CF3)2、LiCF3SO3、LiPF6、LiClO4、LiBF4、LiPO2F2At least one of LiBOB and LiODFB.
Further, in the composite positive electrode, the mass ratio of the positive electrode active material to the second solid sulfide electrolyte, the first conductive material, and the second binder is 50 to 95: 10-45: 0-10: 0-20.
Further, the positive active material is selected from lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganate, cobalt lithium phosphate, lithium manganese nickel oxide, lithium cobaltate, and LiTiS2、LiNiO2At least one of elemental sulfur and a mixture of sulfur and carbon.
Further, the nano coating material is selected from Li3PO4，Al2O3，LiNbO3，LiAlO2，Li3BO3，Li2O-ZrO2、MgO、HfO2，Li2SiO3、B2O3、Li2O、Nb2O5、P2O5、SiO2、Sc2O3、TiO2、ZrO2At least one of (a).
Further, the second adhesive is at least one selected from the group consisting of an ethylene polymer, a styrene polymer, and a butadiene polymer.
Further, the molecular weight of the second binder is 1000-1000000.
Further, the molecular weight of the second binder is 5000-300000.
Further, in the composite anode, the mass ratio of the anode active material to the solid electrolyte, the second conductive material, and the third binder is 40 to 85: 15-60: 0-10: 0-20.
Further, the negative active material is graphite or graphite containing silicon/silicon oxide nanoparticles.
Further, the first, second, and third solid sulfide electrolytes are each independently selected from LPS, LPSCl, LGPS, LSPS, LPSO, and a variant of LPS or LPSCl or LGPS or LSPS or LPSO having a dopant of Si, Ta, Hf, Sc.
Further, the first conductive material and the second conductive material are respectively and independently selected from at least one of Super P, VGCF, carbon nanotubes, acetylene black, Ketjen black and conductive graphene.
Further, the third adhesive is at least one selected from the group consisting of ethylene oxide polymers, ethylene polymers, styrene polymers, and butadiene polymers.
Further, the molecular weight of the third binder is 1000-1000000.
Further, the molecular weight of the third binder is 5000-300000.
Further, the thickness of the buffer layer is 5-50 μm.
Further, the buffer layer comprises a polymer and a third conductive material, the polymer is at least one selected from the group consisting of poly (oxyethylene methacrylate), polysiloxane and polydimethylsiloxane, and the third conductive material is at least one selected from the group consisting of a second lithium salt, a nano ceramic oxide and a nano ceramic sulfide.
Further, the mass ratio of the polymer to the third conductive material is 50-95: 5-50.
Further, the second lithium salt is selected from LiTFSI, LiFSI, LiN (SO)2CF2CF3)2、LiCF3SO3、LiPF6、LiClO4、LiBF4、LiPO2F2At least one of LiBOB and LiODFB.
Further, the buffer layer is stable at a voltage of less than 5v, at-30-150 ℃, and has an ionic conductivity greater than 10 at room temperature-4S/cm。
Compared with the prior art, the solid-state lithium battery has the following advantages:
the solid lithium battery provided by the invention has the solid electrolyte membrane reinforced by the non-woven fabric, the mechanical strength and the telescopic rate of the solid electrolyte membrane can be obviously enhanced by adopting the non-woven fabric, and meanwhile, the solid electrolyte membrane reinforced by the non-woven fabric still has higher ionic conductivity and can be manufactured into a large size; meanwhile, the buffer layer can reduce interface internal resistance and homogenize current density, and a buffer space is provided for volume change of the electrode in the charging and discharging process. . A large number of experiments show that the non-woven fabric reinforced solid-state lithium battery has high mechanical strength and thermal stability, meanwhile, the short circuit of the positive electrode and the negative electrode does not occur in the assembling and using processes of the battery, the preparation success rate is high, the phenomenon that dendrites penetrate through the electrode is remarkably reduced in the using process of the battery, and the non-woven fabric reinforced solid-state lithium battery is very suitable for large-scale industrial production and has remarkable commerciality.
Another object of the present invention is to provide a vehicle to solve the problems of safety and short mileage of the existing vehicles.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a vehicle comprises the solid-state lithium battery.
Compared with the prior art, the vehicle has the following advantages: the vehicle adopts the solid lithium battery which is provided with the non-woven fabric reinforced solid electrolyte membrane, the non-woven fabric can be adopted to obviously enhance the mechanical strength and the scalability of the reinforced solid electrolyte, and meanwhile, the non-woven fabric reinforced solid electrolyte membrane still has higher ionic conductivity and can be manufactured into a large size; meanwhile, the buffer layer can reduce interface internal resistance and homogenize current density, and a buffer space is provided for volume change of the electrode in the charging and discharging process. . A large number of experiments show that the non-woven fabric reinforced solid-state lithium battery has high mechanical strength and thermal stability, meanwhile, the short circuit of the positive electrode and the negative electrode does not occur in the assembling and using processes of the battery, the preparation success rate is high, the phenomenon that dendrites penetrate through the electrode is remarkably reduced in the using process of the battery, and the non-woven fabric reinforced solid-state lithium battery is very suitable for large-scale industrial production and has remarkable commerciality. Therefore, the possibility of safety problems of the vehicle due to the battery is greatly reduced, and simultaneously, the solid-state lithium battery can be manufactured in a large size and has better ionic conductivity, so that the mileage of the vehicle can be effectively prolonged.
Still another object of the present invention is to provide a method for preparing the non-woven fabric reinforced solid electrolyte membrane, which solves the problems of the existing solid lithium battery that the mechanical strength and elongation of the solid electrolyte membrane are too low to realize large-scale production.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
mixing and grinding a first solid sulfide electrolyte, a first adhesive and a first solvent to obtain mixed slurry;
coating the mixed slurry and non-woven fabric on the surface of a base material so as to form a diaphragm layer on the surface of the base material, and blade-coating the diaphragm layer under the inert gas atmosphere so as to obtain a diaphragm sheet;
and carrying out vacuum drying on the diaphragm sheet, and then carrying out hot rolling to obtain the non-woven fabric reinforced solid electrolyte membrane.
Compared with the prior art, the method for preparing the non-woven fabric reinforced solid electrolyte membrane has the following advantages: the first binder is soluble in the first solvent, thereby facilitating an improvement in the effect of mixing the first solid sulfide electrolyte with the first binder and the first solvent. After drying and hot rolling, the first solvent is volatilized, so that the first solid vulcanized electrolyte and the first binder in the non-woven fabric reinforced solid electrolyte membrane are uniformly distributed. The first binder is advantageous for improving the mechanical strength and the stretchability of the non-woven fabric-reinforced solid electrolyte membrane and making the distribution of the first solid sulfide electrolyte more uniform. The non-woven fabric can further improve the mechanical strength and the scalability of the non-woven fabric reinforced solid electrolyte membrane, and simultaneously, the non-woven fabric reinforced solid electrolyte membrane still has higher ionic conductivity, and the non-woven fabric reinforced solid electrolyte membrane can be manufactured into a large size. The whole process is simple and easy for commercial production.
Further, the first solid sulfide electrolyte is washed with a second solvent before the first solid sulfide electrolyte, the first binder and the first solvent are mixed and ground, and the washed first solid sulfide electrolyte is dried in a vacuum environment.
Further, the first solid sulfide electrolyte, the first binder and the first solvent are mixed and ground for 0.5-1h at 100-300 rpm.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural view of a solid-state lithium battery according to an embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a method of making a nonwoven fabric reinforced solid state electrolyte membrane according to one embodiment of the invention;
FIG. 3 is a schematic flow diagram of a method of making a non-woven fabric reinforced solid state electrolyte membrane according to yet another embodiment of the present invention;
fig. 4 is a schematic structural view of a single-layer solid-state lithium battery in example 1 of the present invention;
FIG. 5 is a view showing a state after the mechanical strength test of a nonwoven fabric-reinforced solid electrolyte membrane in example 1 of the present invention;
FIG. 6 is an SEM image of a nonwoven fabric-reinforced solid electrolyte membrane in example 1 of the present invention;
FIG. 7 is an ion conductivity of a non-woven fabric-reinforced solid electrolyte membrane in example 1 of the present invention;
FIG. 8 shows LiNbO-containing molecules in example 1 of the present invention3SEM inspection image of coating NCM 811;
FIG. 9 shows LiNbO-containing molecules in example 1 of the present invention3EDX inspection image of coating NCM 811;
fig. 10 is a schematic structural view of a single-layer solid-state lithium battery in example 2 of the invention;
fig. 11 is a schematic structural view of a two-layer solid-state lithium battery according to embodiment 3 of the present invention;
fig. 12 is a schematic structural diagram of a two-layer solid-state lithium battery in embodiment 4 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In one aspect of the present invention, the present invention provides a solid-state lithium battery, which includes, according to an embodiment of the present invention, with reference to fig. 1: a non-woven fabric-reinforced solid electrolyte membrane 100, a positive electrode 200, a negative electrode 300, and a buffer layer 400.
According to an embodiment of the present invention, a non-woven fabric-reinforced solid electrolyte membrane includes: a first solid sulfide electrolyte, a nonwoven fabric, and a first binder. The inventors found that the first binder is advantageous in improving the mechanical strength and the stretchability of the nonwoven fabric-reinforced solid electrolyte membrane and making the distribution of the first solid sulfide electrolyte more uniform. The non-woven fabric can further improve the mechanical strength and the scalability of the non-woven fabric reinforced solid electrolyte membrane, and simultaneously, the non-woven fabric reinforced solid electrolyte membrane still has higher ionic conductivity, and the non-woven fabric reinforced solid electrolyte membrane can be manufactured into a large size. The whole process is simple and easy for commercial production.
According to one embodiment of the present invention, the tensile strength of the non-woven fabric-reinforced solid electrolyte membrane is 100-10000N/cm2And the elongation is 0-50%. Therefore, the non-woven fabric reinforced solid electrolyte membrane has higher tensile strength and elongation compared with the existing solid electrolyte membrane, is beneficial to manufacturing the large-size non-woven fabric reinforced solid electrolyte membrane, improves the energy density of a battery, and is convenient for commercial production and use of a solid lithium battery.
According to still another embodiment of the present invention, in the non-woven fabric-reinforced solid electrolyte membrane, the mass ratio of the first solid sulfide electrolyte to the non-woven fabric, the first binder may be 80 to 97: 0.01-20: 3-10. The inventors found that too high contents of the nonwoven fabric and the first binder cause a large decrease in the ionic conductivity of the solid electrolyte membrane, and that too low contents of the nonwoven fabric or the first binder do not provide sufficient electrolyte membrane strength.
According to yet another embodiment of the invention, the first solid sulfide electrolyte may be selected from at least one of LPS, LPSCl, LGPS, LSPS, LPSO. Wherein LPS is xLi2S·(1-x)P2S5LPSCl is Li6PS5Cl, LGPS is Li10GeP2S12LSPS is Li10SnP2S12LPSO is 70Li2S·29P2S5·1P2O5. It should be noted that the first solid sulfide electrolyte may also be a variant with dopants of Si, Ta, Hf, Sc, etc. in LPS or LPSCl or LGPS or LSPS or LPSO.
According to yet another embodiment of the present invention, the nonwoven fabric is at least one of a PP-based nonwoven fabric, a PE-based nonwoven fabric, a PET-based nonwoven fabric, a PAN-based nonwoven fabric, a PTFE-based nonwoven fabric, and a Celgard nonwoven fabric. The inventors have found that a non-woven fabric of the above type has a low negative effect on the ionic conductivity of the first solid sulfide electrolyte, and that the mechanical strength, tensile strength and elongation of the first solid sulfide electrolyte can be improved while the first solid sulfide electrolyte still has a high ionic conductivity.
According to yet another embodiment of the invention, the grammage of the nonwoven may be 1-10g/m2The porosity can be 50-95%, the thickness can be 10-50 μm, and the tensile strength can be 200-4500N/cm2. The inventors found that when the areal density of the nonwoven fabric is too small, the porosity is too high, and when the thickness is too small, the tensile strength is too small; too high areal density, too low porosity and too high thickness can result in the first solid sulfide electrolyte not penetrating the nonwoven to form a film.
According to still another embodiment of the present invention, the first binder may be at least one of an ethylene oxide-based polymer, a vinyl-based polymer, a vinylidene fluoride-based polymer, a styrene-based polymer, and a butadiene-based polymer. The inventors have found that the first binder of the above type can improve the distribution uniformity of the first solid sulfide electrolyte in the nonwoven fabric-reinforced solid electrolyte membrane to some extent, improve the ionic conductivity of the nonwoven fabric-reinforced solid electrolyte membrane, and at the same time, can further improve the mechanical strength of the nonwoven fabric-reinforced solid electrolyte membrane.
According to yet another embodiment of the present invention, the molecular weight of the first binder may be 100000-1000000. The inventors found that when the molecular weight of the binder is too low, the viscosity is poor, and when the molecular weight is too high, the binder is not easily dissolved in an organic solvent.
According to another embodiment of the present invention, the non-woven fabric reinforced solid electrolyte may further comprise a first lithium salt, and the first lithium salt may be selected from LiTFSI, LiFSI, LiN (SO)2CF2CF3)2、LiCF3SO3、LiPF6、LiClO4、LiBF4、LiPO2F2At least one of LiBOB and LiODFB. It is noted that the first lithium salt needs to have good compatibility with the first solid sulfide electrolyte. In practice, the selection can be made by: and (2) mixing the first lithium salt and the first solid sulfide electrolyte, and dry-pressing the mixture into a sheet to obtain a sheet sulfide electrolyte containing the lithium salt, measuring the AC impedance and the cyclic voltammetry impedance of the sheet sulfide electrolyte containing the lithium salt under the pressure of 100-400MPa, wherein if the AC impedance and the cyclic voltammetry impedance of the sheet sulfide electrolyte containing the lithium salt are smaller than the AC impedance and the cyclic voltammetry impedance of the first solid sulfide electrolyte sheet without the lithium salt, the selected first lithium salt has good compatibility with the first solid sulfide electrolyte. The addition of the first lithium salt contributes to the improvement of the ionic conductivity of the non-woven fabric-reinforced solid electrolyte membrane.
According to an embodiment of the present invention, the positive electrode 200 includes an aluminum foil 210 and a composite positive electrode 220 including: the composite material comprises a positive active material, a nano coating material, a second solid sulfide electrolyte, a first conductive material and a second adhesive, wherein the nano coating material is coated on the surface of the positive active material. Specifically, in the solid-state lithium battery, when the battery is a single-layer battery, that is, the battery only comprises one positive electrode and one negative electrode, only one side of an aluminum foil needs to be coated with a composite positive electrode; when the battery is a double-layer or multilayer battery, namely the battery comprises two or more anodes and two or more cathodes, the composite anodes can be coated on two sides of the aluminum foil, so that the sharing of the aluminum foil is realized, the energy density of the battery is improved, the volume of the battery is reduced under the same battery capacity, and the commercial application is facilitated. For the above positive electrode, the following method can be employed for preparation: coating the surface of the positive active material with the nano coating material to obtain the positive active material containing the coating; mixing and wet-milling the coating-containing positive electrode active material, a second solid sulfide electrolyte, a second adhesive, a first conductive material and a third solvent to obtain positive electrode mixed slurry; coating the obtained anode mixed slurry on an aluminum foil, and performing vacuum drying to obtain an anode plate; and rolling the positive plate to obtain the positive electrode. The carbon layer of the aluminum foil used is not more than 1 μm thick, and an excessively thick carbon layer affects the conductivity of the positive electrode. The temperature during rolling can be 50-70 ℃, the rolling temperature is not favorable for positive electrode densification, and the second binder can be damaged when the rolling temperature is too high. Further, when the coated positive electrode active material is mixed and wet-milled with the second solid sulfide electrolyte, the second binder, the first conductive material and the third solvent, the second solid sulfide electrolyte, the second binder and the third solvent may be mixed and wet-milled for a long time, and then the coated positive electrode active material and the first conductive material may be added to the mixed and wet-milled for a short time. Thus, damage to the coating layer on the surface of the coated positive electrode active material can be avoided. The above-mentioned third solvent is an organic solvent, and the third solvent can dissolve the second binder while having a small negative influence on the second solid sulfide electrolyte. It should be noted that the specific type of the third solvent can be selected by those skilled in the art in practical process according to the second solid sulfide electrolyte and the second binder, and may be at least one of ketones, amines, esters, ethers, and alkanes, for example. The inventors found that the second binder is soluble in the third solvent, and therefore, the mixing effect of the second solid sulfide electrolyte with the second binder, the third solvent, the coated positive electrode active material, and the first conductive agent is advantageously improved. After drying, the third solvent is volatilized, so that the coating-containing positive active material, the second solid sulfide electrolyte, the first conductive agent and the first adhesive in the composite positive electrode are uniformly distributed, the energy density of the positive electrode is favorably improved, and the cycle service life of the battery is prolonged. Meanwhile, the whole preparation process is simple in process, large-size manufacturing is easy to realize, and commercialization is easy to realize. The inventors have found that the nanocoating material has a high dielectric constant, prevents the positive electrode active material from reacting with the second solid sulfide electrolyte, does not restrict diffusion of lithium ions, and does not react with the second solid sulfide electrolyte.
According to an embodiment of the present invention, in the composite positive electrode, the mass ratio of the positive electrode active material to the second solid sulfide electrolyte, the first conductive material, and the second binder may be 50 to 95: 10-45: 0-10: 0-20. It should be noted that the specific proportions of the positive electrode active material, the second solid sulfide electrolyte, the first conductive material, and the second binder can be selected and optimized by those skilled in the art according to actual needs.
According to still another embodiment of the present invention, the positive active material may be lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganate, lithium cobalt phosphate, lithium manganese nickel oxide, lithium cobaltate, LiTiS2、LiNiO2At least one of elemental sulfur and a mixture of sulfur and carbon. Specifically, when lithium is contained in the negative electrode, the positive electrode active material may be elemental sulfur or a sulfur-carbon mixture.
According to yet another embodiment of the invention, the nanocoating material may be Li3PO4，Al2O3，LiNbO3，LiAlO2，Li3BO3，Li2O-ZrO2、MgO、HfO2，Li2SiO3、B2O3、Li2O、Nb2O5、P2O5、SiO2、Sc2O3、TiO2、ZrO2At least one of (a).
According to yet another embodiment of the invention, the second solid sulfide electrolyte may be at least one of LPS, LPSCl, LGPS, LSPS, LPSO and LPS or LPSCl or LGPS or LSPS or LPSO with a Si, Ta, Hf, Sc dopant variant.
According to still another embodiment of the present invention, the first conductive material may be at least one selected from Super P, VGCF, carbon nanotube, acetylene black, ketjen black, conductive graphene. According to still another embodiment of the present invention, the second adhesive may be at least one of a vinyl polymer, a styrenic polymer, a butadiene-based polymer. The molecular weight of the second binder may be 1000-.
According to an embodiment of the present invention, the negative electrode 300 includes a current collector 310 and a negative electrode material 320, the current collector is a copper foil or a nickel foil, and the negative electrode material is lithium or indium or a lithium-indium alloy or a composite negative electrode. Specifically, in the solid-state lithium battery, when the battery is a single-layer battery, that is, the battery only comprises one positive electrode and one negative electrode, only one side of the current collector is coated with the composite negative electrode; when the battery is a double-layer or multilayer battery, namely the battery comprises two or more anodes and two or more cathodes, the composite cathodes can be coated on the two sides of the current collector, so that the sharing of the current collector is realized, the energy density of the battery is improved, the volume of the battery is reduced under the same battery capacity, and the commercial application is facilitated.
According to an embodiment of the present invention, when the anode material is a composite anode, the composite anode includes: a negative active material, a solid electrolyte, a second conductive material, and a third binder. For the negative electrode, the following method can be used for preparation: mixing and grinding a negative electrode active material, a solid electrolyte, a second conductive material, a third binder and a fourth solvent to obtain negative electrode mixed slurry; coating the negative electrode mixed slurry on a current collector, and performing vacuum drying to obtain a negative electrode piece; the negative electrode sheet was subjected to roll pressing to obtain a negative electrode. The temperature of the rolling may be 50-60 degrees celsius. When the negative electrode active material is mixed and ground with the solid electrolyte, the second conductive material, the third binder, and the fourth solvent, the third binder may be first dissolved in the fourth solvent, and then the negative electrode active material, the solid electrolyte, and the second conductive material may be added. The above-mentioned fourth solvent is an organic solvent, and the fourth solvent can dissolve the third binder while having less negative influence on the solid electrolyte. It should be noted that the specific type of the fourth solvent may be selected by those skilled in the art in practical process according to the solid electrolyte and the third binder, and may be at least one of ketones, amines, esters, ethers, and alkanes, for example. The inventors found that, since the third binder is dissolved in the fourth solvent, it is advantageous to improve the effect of mixing the negative electrode active material with the solid electrolyte, the second conductive material, the third binder, and the fourth solvent. After drying, the fourth solvent is volatilized, so that the negative active material, the solid electrolyte, the second conductive material and the third adhesive in the composite negative electrode are uniformly distributed, the energy density of the negative electrode is favorably improved, and the cycle service life of the battery is prolonged. Meanwhile, the whole preparation process is simple in process, large-size manufacturing is easy to realize, and commercialization is easy to realize.
According to still another embodiment of the present invention, in the composite anode, a mass ratio of the anode active material to the solid electrolyte, the second conductive material, and the third binder may be 40 to 85: 15-60: 0-10: 0-20.
According to yet another embodiment of the present invention, the negative active material may be graphite or graphite containing silicon/silicon oxide nanoparticles. The inventors have found that the addition of silicon/silicon oxide nanoparticles to graphite can increase the specific capacity of the negative active material while maintaining relatively good cycling performance.
According to yet another embodiment of the invention, the solid electrolyte may be at least one of a third solid sulfide electrolyte and a solid polymer electrolyte, wherein the third solid sulfide electrolyte may be at least one of LPS, LPSCl, LGPS, LSPS, LPSO and LPS or LPSCl or LGPS or LSPS or LPSO with a Si, Ta, Hf, Sc dopant variant. The solid polymer electrolyte may be at least one of PEO, PPC, PVDF.
According to still another embodiment of the present invention, the second conductive material may be at least one of Super P, VGCF, carbon nanotube, acetylene black, ketjen black, conductive graphene. According to still another embodiment of the present invention, the third adhesive may be at least one of an ethylene oxide-based polymer, an ethylene-based polymer, a styrene-based polymer, and a butadiene-based polymer. The molecular weight of the third binder is 1000-.
According to an embodiment of the present invention, the buffer layer includes a polymer and a third conductive material, the polymer may be at least one selected from the group consisting of poly (oxyethylene methacrylate), polysiloxane, and polydimethylsiloxane, and the third conductive material may be at least one selected from the group consisting of a second lithium salt, a nano ceramic oxide, and a nano ceramic sulfide. Wherein the second lithium salt is in contact with the first solid sulfide electrolyte and/or the second solid sulfide electrolyteThe sulfide electrolyte and/or the solid electrolyte are stable. A buffer layer may be coated on the composite cathode and/or anode material to separate the composite cathode and/or anode material from the non-woven fabric reinforced solid state electrolyte membrane. In the actual cell assembly process, the buffer layer should be coated in a specific manner so that the entire cell has low interfacial resistance and is easy to assemble. The nano ceramic oxide may be LLZO (Li)7La3Zr2O12)、LATP(Li1.4Al0.4Ti1.6(PO4)3) The nanoceramic sulfide may be LGPS (Li)10GeP2S12) LPSO, etc., the synergistic effect of the nano-ceramic oxide and nano-ceramic sulfide and polymer can greatly increase the ionic conductivity of the buffer layer. The buffer layer is a film and can be formed by a dry method or a wet method. Specifically, the dry method is as follows: and mixing the polymer and the third conductive material to obtain a buffer layer mixed material, and carrying out hot rolling on the obtained buffer layer mixed material to obtain the buffer layer. Wherein the hot rolling may be performed by sandwiching the buffer layer mixture between films which are non-adhesive and non-reactive with the buffer layer mixture, and the hot rolling may be performed at 35 to 45 degrees celsius. The wet method comprises the following steps: and dissolving the polymer and the third conductive material in a fifth solvent to obtain buffer layer mixed slurry, coating the buffer layer mixed slurry on a substrate, drying in vacuum, and blade-coating the buffer layer sheets on the aggregate to obtain the buffer layer. When the negative electrode is lithium or indium or a lithium indium alloy, the mixed slurry may be directly coated on the negative electrode. The inventor finds that the buffer layer can reduce the internal resistance of the interface, homogenize the current density and provide a buffer space for the volume change of the electrode in the charging and discharging processes.
According to an embodiment of the present invention, in the buffer layer, the mass ratio of the polymer to the third conductive material may be 95 to 50: 5-50. The inventors have found that the mass ratio of the polymer to the third conductive material in the above range can provide the buffer layer with superior ionic conductivity, thermal stability and mechanical properties.
According to still another embodiment of the present invention, the buffer layer may have a thickness of 5 to 50 μm. The inventors found that the buffer layer is too thin to serve as a buffer, and too thick affects the rate and other properties of the battery.
According to still another embodiment of the present invention, the second lithium salt may be LiTFSI, LiFSI, LiN (SO)2CF2CF3)2、LiCF3SO3、LiPF6、LiClO4、LiBF4、LiPO2F2At least one of LiBOB and LiODFB.
According to yet another embodiment of the present invention, the buffer layer is stable at a voltage of less than 5v, stable at-30-150 ℃, and has an ionic conductivity of greater than 10 at room temperature-4S/cm. That is, the buffer layer in the present application has high voltage resistance, wide thermal stability and certain ionic conductivity, and thus, the buffer layer can improve the electrochemical performance and cycle performance of the battery.
According to the embodiment of the invention, the solid lithium battery is provided with the non-woven fabric reinforced solid electrolyte membrane, the non-woven fabric is adopted, so that the mechanical strength and the telescopic rate of the reinforced solid electrolyte membrane can be obviously improved, and meanwhile, the non-woven fabric reinforced solid electrolyte membrane still has higher ionic conductivity and can be manufactured into a large size; meanwhile, the buffer layer can reduce interface internal resistance and homogenize current density, and a buffer space is provided for volume change of the electrode in the charging and discharging process. A large number of experiments show that the non-woven fabric reinforced solid-state lithium battery has high mechanical strength and thermal stability, meanwhile, the short circuit of the positive electrode and the negative electrode does not occur in the assembling and using processes of the battery, the preparation success rate is high, the phenomenon that dendrites penetrate through the electrode is remarkably reduced in the using process of the battery, and the non-woven fabric reinforced solid-state lithium battery is very suitable for large-scale industrial production and has remarkable commerciality.
In yet another aspect of the invention, a vehicle is provided that includes the above-described enhanced solid state lithium battery, according to an embodiment of the invention. The inventor finds that, because the vehicle adopts the solid lithium battery, the solid lithium battery is provided with the non-woven fabric reinforced solid electrolyte membrane, the mechanical strength and the scalability of the solid electrolyte membrane can be obviously enhanced by adopting the non-woven fabric, and meanwhile, the non-woven fabric reinforced solid electrolyte membrane still has higher ionic conductivity and can be manufactured into a large size; meanwhile, the buffer layer can reduce interface internal resistance and homogenize current density, and a buffer space is provided for volume change of the electrode in the charging and discharging process. A large number of experiments show that the non-woven fabric reinforced solid-state lithium battery has high mechanical strength and thermal stability, meanwhile, the short circuit of the positive electrode and the negative electrode does not occur in the assembling and using processes of the battery, the preparation success rate is high, the phenomenon that dendrites penetrate through the electrode is remarkably reduced in the using process of the battery, and the non-woven fabric reinforced solid-state lithium battery is very suitable for large-scale industrial production and has remarkable commerciality. Therefore, the possibility of safety problems of the vehicle due to the battery is greatly reduced, and simultaneously, the solid-state lithium battery can be manufactured in a large size and has better ionic conductivity, so that the mileage of the vehicle can be effectively prolonged.
In yet another aspect of the present invention, the present invention provides a method of preparing the above-described non-woven fabric-reinforced solid electrolyte membrane, according to an embodiment of the present invention, with reference to fig. 2, the method including:
s100: mixing and grinding a first solid sulfide electrolyte, a first adhesive and a first solvent
In this step, the first solid sulfide electrolyte, the first binder, and the first solvent are mixed and ground to obtain a mixed slurry. Further, the first binder may further include a first lithium salt. The first binder is soluble in a first solvent, and when the first binder contains a first lithium salt, the first lithium salt is also soluble in the first solvent, the first solvent is an organic solvent, and the first solvent has less adverse effect on the first solid sulfide electrolyte. It should be noted that the specific type of the first solvent can be selected by those skilled in the art in practical process according to the first solid sulfide electrolyte and the first binder, and may be at least one of ketones, amines, esters, ethers, and alkanes, for example. Table 1 shows the conductivity of the four first solid sulfide electrolytes after being treated with anisole at a long temperature and 80 ℃, and it can be seen from table 1 that, at normal temperature, the conductivity of LPSCl after being treated with anisole decreases by 1%, the conductivity of LGPS after being treated with anisole decreases by 24%, the conductivity of LSPS after being treated with anisole increases by 15%, and the conductivity of LPSO after being treated with anisole decreases by 46%; at 80 ℃, the conductivity of LPSCl after anisole treatment is reduced by 24%, the conductivity of LGPS after anisole treatment is increased by 26%, the conductivity of LSPS after anisole treatment is reduced by 32%, and the conductivity of LPSO after anisole treatment is reduced by 81%. That is, when the first solid sulfide electrolyte is LPSO, the use of anisole as the first solvent has a large influence on LPSO, and is not suitable for use as a solvent for LPSO.
TABLE 1 conductivity of four first solid sulfide electrolytes before and after treatment with anisole at long temperature and 80 deg.C
Figure BDA0001955076690000101
Figure BDA0001955076690000111
The inventors found that it is advantageous to improve the mixing effect of the first solid sulfide electrolyte with the first binder and the first solvent by mixing and grinding the first solid sulfide electrolyte with the first binder and the first solvent, wherein the first binder is dissolved in the first solvent. So that the first solid sulfide electrolyte, the first binder and the first solvent in the mixed slurry are uniformly distributed, and the improvement of the ion conductivity of the non-woven fabric reinforced solid electrolyte membrane is facilitated. The first binder is advantageous for improving the mechanical strength and the stretchability of the non-woven fabric-reinforced solid electrolyte membrane and making the distribution of the first solid sulfide electrolyte more uniform.
According to one embodiment of the present invention, the first solid sulfide electrolyte, the first binder, and the first solvent are mixed and ground for 0.5-1h at 100-300 rpm. The inventors have found that too low a mixing and grinding speed and too short a time can result in uneven mixing; too high a grinding speed and too long a grinding time can cause the material particles to be destroyed.
S200: coating the mixed slurry and non-woven fabric on the surface of a substrate
In this step, the mixed slurry and the nonwoven fabric are applied to the surface of the substrate to form a separator layer on the surface of the substrate, and the separator layer is blade-coated under an inert gas atmosphere to obtain a separator sheet. Specifically, when the mixed slurry and the non-woven fabric are coated on the surface of the base material, the non-woven fabric and the mixed slurry can be directly mixed and then coated on the surface of the base material and/or a layer of non-woven fabric is laid in the mixed slurry. The inventors found that the nonwoven fabric can further improve the mechanical strength and the stretchability of the nonwoven fabric-reinforced solid electrolyte membrane, while allowing the nonwoven fabric-reinforced solid electrolyte membrane to still have a high ionic conductivity and allowing the nonwoven fabric-reinforced solid electrolyte membrane to be fabricated in a large size.
S300: vacuum drying the diaphragm sheet, and hot rolling
In this step, the separator sheet is dried in vacuum and then hot-rolled to obtain a non-woven fabric-reinforced solid electrolyte membrane. The inventors found that the first solvent is volatilized after drying and hot rolling, so that the first solid-state vulcanized electrolyte and the first binder are uniformly distributed in the nonwoven fabric-reinforced solid electrolyte membrane. After hot rolling, the structure of the solid electrolyte membrane reinforced by the non-woven fabric is more compact, which is beneficial to reducing the volume of the solid electrolyte membrane reinforced by the non-woven fabric.
According to an embodiment of the present invention, the temperature of the hot rolling may be 60 to 80 ℃ and the time may be 0.5 to 2 hours.
According to the embodiment of the present invention, the method of manufacturing the above-described nonwoven fabric-reinforced solid electrolyte membrane is advantageous in improving the mixing effect of the first solid sulfide electrolyte with the first binder and the first solvent because the first binder is dissolved in the first solvent. After drying and hot rolling, the first solvent is volatilized, so that the first solid vulcanized electrolyte and the first binder in the non-woven fabric reinforced solid electrolyte membrane are uniformly distributed. The first binder is advantageous for improving the mechanical strength and the stretchability of the non-woven fabric-reinforced solid electrolyte membrane and making the distribution of the first solid sulfide electrolyte more uniform. The non-woven fabric can further improve the mechanical strength and the scalability of the non-woven fabric reinforced solid electrolyte membrane, and simultaneously, the non-woven fabric reinforced solid electrolyte membrane still has higher ionic conductivity, and the non-woven fabric reinforced solid electrolyte membrane can be manufactured into a large size. The whole process is simple and easy for commercial production.
According to an embodiment of the present invention, referring to fig. 3, before the mixed grinding of the first solid sulfide electrolyte and the first binder, the first solvent, may further include:
s400: washing the first solid sulfide electrolyte with a second solvent, and drying the washed first solid sulfide electrolyte in a vacuum environment
In the step, the first solid sulfide electrolyte is washed by the second solvent, and the washed first solid sulfide electrolyte is dried in a vacuum environment, so that the first solid sulfide electrolyte with a clean surface and uniform particle size can be obtained, and the improvement of the ion conductivity of the non-woven fabric reinforced solid electrolyte membrane is facilitated. Specifically, the second solvent is an organic solvent, and the second solvent has less negative influence on the first solid sulfide electrolyte. It should be noted that the specific type of the second solvent can be selected by those skilled in the art according to the first solid sulfide electrolyte in practical process, and may be at least one of ketones, amines, esters, ethers, and alkanes, for example.
It should be noted that the properties and characteristics of the non-woven fabric reinforced solid electrolyte membrane described above also exist in the preparation of the non-woven fabric reinforced solid electrolyte membrane, and are not described in detail herein.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Example 1
A single-layer solid-state lithium battery is shown in figure 4, and comprises the following components in sequence from top to bottom: copper foil 310 (thickness: 8 μm), lithium negative electrode material 320 (thickness: 50 μm), buffer layer 400 (thickness: 25 μm), non-woven fabric-reinforced solid electrolyte membrane 100 (thickness: 80 μm), composite positive electrode 220 (thickness: 100 μm) and aluminum foil 210 (thickness: 6 μm).
Wherein:
the buffer layer comprises poly (oxyethylene methacrylate) and LiTSFI, and the mass ratio of poly (oxyethylene methacrylate) to LITFSI is 4: 1.
the non-woven fabric reinforced solid electrolyte membrane comprises LPSCl and PP-based non-woven fabric (the gram weight is 1 g/m)2A porosity of 95%, a thickness of 10 μm and a tensile strength of 1000N/cm2) And polyethylene oxide (molecular weight 100000), the mass ratio of LPSCl, PP-based nonwoven fabric and polyethylene oxide being 95: 2: 3, the preparation method of the non-woven fabric reinforced solid electrolyte membrane comprises the following steps: firstly, grinding LPSCl, polyethylene oxide and CHO for 0.5h at 100rpm to obtain mixed slurry; then coating the mixed slurry and PP-based non-woven fabric on the surface of a base material so as to form a diaphragm layer on the surface of the base material, and blade-coating the diaphragm layer in an argon atmosphere to obtain a diaphragm sheet; the separator sheet was vacuum-dried at 80 ℃ for about 14 hours and then hot-rolled to obtain a non-woven fabric-reinforced solid electrolyte membrane, which was not torn or perforated by placing the non-woven fabric-reinforced solid electrolyte membrane between 2 stainless steel pistons under a high pressure of 200MPa after mechanical strength testing, and the tested non-woven fabric-reinforced solid electrolyte membrane was as shown in fig. 5. SEM images of the nonwoven fabric-reinforced solid electrolyte membrane are shown in fig. 6. The ionic conductivity is shown in FIG. 7. The tensile strength of the non-woven fabric reinforced solid electrolyte membrane is 1000N/m2The elongation thereof was 20%.
The composite positive electrode includes: LiNbO3Coated NCM811, LPSCl, SP + VGCF and PVDF1&B2，LiNbO3Coated NCM811 with LPSCl, SP + VGCF and PVDF1&The mass ratio of B2 is 60: 32: 3: 5. LiNbO3The coated NCM811 was subjected to SEM examination and EDX examination, respectively, and the results were as follows: the SEM image is shown in FIG. 8, and it can be seen from FIGS. 8(a-c) that LiNbO is present3The average particle size of the coated NCM811 was 14 μm, as can be seen from FIG. 8(d), in LiNbO3Coated NCM811 particles on LiNbO3The thickness of the coating is less than 10 nm. The EDX spectrum is shown in FIG. 9, the specific element data is shown in Table 2, and the fact that the surface of NCM811 particles has LiNbO can be further proved by the EDX spectrum shown in FIG. 9 and the specific element data shown in Table 23And (4) coating.
TABLE 2 LiNbO3EDX analysis data of coated NCM811 particles
Element(s) Of the linear type Key parameter Absorption/correction Mass fraction% ∑(％)
O K 2.028 1.00 40.77 0.13
Mn K 1.144 1.00 6.76 0.05
Co K 1.175 1.00 6.12 0.05
Ni K 1.151 1.00 43.67 0.12
Nb L 1.799 1.00 2.68 0.08
The single-layer solid lithium battery is obtained by pressing and molding the negative electrode, the buffer layer, the non-woven fabric reinforced solid electrolyte membrane and the positive electrode at 60 ℃ and 5MPa, wherein in the rolling process, the high molecular compounds in the substances serve as binders, so that the lithium negative electrode material layer in the negative electrode is bonded with one side of the buffer layer, the other side of the buffer layer is bonded with one side of the non-woven fabric reinforced solid electrolyte membrane, and the other side of the non-woven fabric reinforced solid electrolyte membrane is bonded with the composite positive electrode in the positive electrode. The single-layer solid-state lithium battery has the advantages that the short circuit of the anode and the cathode does not occur in the assembling and using processes, the preparation success rate is high, the phenomenon that dendrites penetrate through the electrode is obviously reduced in the using process of the battery, the single-layer solid-state lithium battery is very suitable for large-scale industrial production, and the single-layer solid-state lithium battery has obvious commercial property.
Example 2
A single-layer solid-state lithium battery, whose structural diagram is shown in fig. 10, comprises, from top to bottom: copper foil 310 (8 μm thick), composite negative electrode 320 (120 thick), buffer layer 400 (35 μm thick), non-woven fabric-reinforced solid electrolyte membrane 100 (100 thick), composite positive electrode 220 (80 thick) and aluminum foil 210 (6 μm thick). Wherein:
the composite anode includes: graphite, LGPS, SP and PEO, wherein the mass ratio of the graphite to the LGPS, the SP and the PEO is 70: 25: 3: 2.
the buffer layer comprises polysiloxane and LiBOB, and the mass ratio of the polysiloxane to the LiBOB is 75: 25.
the non-woven fabric reinforced solid electrolyte membrane comprises LGPS and PE-based non-woven fabric (the gram weight is 3 g/m)2Porosity of 80%, thickness of 20 μm, and tensile strength of 1000N/cm2) And polyethylene oxide (molecular weight of 600000), the mass ratio of LGPS, PE-based nonwoven fabric, and polyethylene oxide being 90: 5: 5, the preparation method of the non-woven fabric reinforced solid electrolyte membrane comprises the following steps: firstly, grinding LGPS, polyethylene oxide and CHO for 0.6h at 200rpm to obtain mixed slurry; then coating the mixed slurry and the PE-based non-woven fabric on the surface of a base material so as to form a diaphragm layer on the surface of the base material, and blade-coating the diaphragm layer in an argon atmosphere to obtain a diaphragm sheet; the separator sheet was vacuum-dried at 75 degrees celsius for about 14 hours and then hot-rolled to obtain a non-woven fabric-reinforced solid electrolyte membrane.
The composite positive electrode includes: SiO 22Coated NCM622, LGPS, SP + CNT and PVDF2, SiO2The mass ratio of coated NCM622, LGPS, SP + CNT and PVDF2 was 82: 15: 1: 2.
the single-layer solid lithium battery is obtained by pressing and molding the negative electrode, the buffer layer, the non-woven fabric reinforced solid electrolyte membrane and the positive electrode at 70 ℃ and 5MPa, wherein in the rolling process, the high molecular compounds in the substances serve as binders to enable the composite negative electrode in the negative electrode to be bonded with one side of the buffer layer, the other side of the buffer layer is bonded with one side of the non-woven fabric reinforced solid electrolyte membrane, and the other side of the non-woven fabric reinforced solid electrolyte membrane is bonded with the composite positive electrode in the positive electrode. The single-layer solid-state lithium battery has the advantages that the short circuit of the anode and the cathode does not occur in the assembling and using processes, the preparation success rate is high, the phenomenon that dendrites penetrate through the electrode is obviously reduced in the using process of the battery, the single-layer solid-state lithium battery is very suitable for large-scale industrial production, and the single-layer solid-state lithium battery has obvious commercial property.
Example 3
A double-layer battery sharing copper foil, the structural schematic diagram of which is shown in fig. 11, and the double-layer battery sequentially comprises from top to bottom: an aluminum foil 210 (thickness: 8 μm), a composite positive electrode 220 (thickness: 90 μm), a buffer layer 400 (thickness: 45 μm), a nonwoven fabric-reinforced solid electrolyte membrane 100 (thickness: 75 μm), an indium negative electrode material 320 (thickness: 50 μm), a copper foil 310 (thickness: 6 μm), an indium negative electrode material 320 (thickness: 50 μm), a nonwoven fabric-reinforced solid electrolyte membrane 100 (thickness: 75 μm), a buffer layer 400 (thickness: 45 μm), a composite positive electrode 220 (thickness: 90 μm), and an aluminum foil 210 (thickness: 8 μm).
The composite positive electrode includes: li3PO4Coated LiNiO2LSPS, ketjen black + conductive graphene and PVDF3, Li3PO4Coated LiNiO2The mass ratio of the LSPS to the Ketjen black to the conductive graphene to the PVDF3 is 65: 30: 3: 2.
the buffer layer comprises polysiloxane and LiPF6Polysiloxanes with LiPF6The mass ratio of (A) to (B) is 80: 20.
the non-woven fabric reinforced solid electrolyte membrane comprises LSPS and PET-based non-woven fabric (the gram weight is 6 g/m)2A porosity of 90%, a thickness of 35 μm and a tensile strength of 2500N/cm2) And polyethylene oxide (molecular weight 800000), the mass ratio of LSPS, PET-based nonwoven fabric, and polyethylene oxide being 92: 5: 3, the preparation method of the non-woven fabric reinforced solid electrolyte membrane comprises the following steps: firstly, grinding LSPS, polyethylene oxide and cyclohexanone for 1h at 300rpm to obtain mixed slurry; then coating the mixed slurry and PET-based non-woven fabric on the surface of a base material so as to form a diaphragm layer on the surface of the base material, and blade-coating the diaphragm layer in an argon atmosphere to obtain a diaphragm sheet; the separator sheet was vacuum-dried at 80 degrees celsius for about 13 hours and then hot-rolled to obtain a non-woven fabric-reinforced solid electrolyte membrane.
And indium cathode materials are arranged on two sides of the copper foil.
The method comprises the following steps of pressing and molding a positive electrode, a buffer layer, a non-woven fabric reinforced solid electrolyte membrane, a negative electrode, a non-woven fabric reinforced solid electrolyte membrane, a buffer layer and a positive electrode at 80 ℃ and 5MPa, sharing copper foil to obtain the double-layer solid lithium battery, wherein in the rolling process, a high molecular compound in each substance serves as a binder to bond the composite positive electrode in the positive electrode with one side of the buffer layer, the other side of the buffer layer is bonded with one side of the non-woven fabric reinforced solid electrolyte membrane, and the other side of the non-woven fabric reinforced solid electrolyte membrane is bonded with the composite negative electrode in the negative electrode. The double-layer battery with the shared copper foil has the advantages that the short circuit of the anode and the cathode does not occur in the assembling and using processes, the preparation success rate is high, the phenomenon that dendrites penetrate through the electrode is obviously reduced in the using process of the battery, the double-layer battery is very suitable for large-scale industrial production, and the double-layer battery with the shared copper foil has obvious commercial property.
Example 4
A double-layer cell sharing aluminum foil, whose structural schematic diagram is shown in fig. 12, and comprises, from top to bottom: copper foil 310 (thickness: 5 μm), lithium indium alloy negative electrode material 320 (thickness: 40 μm), non-woven fabric-reinforced solid electrolyte membrane 100 (thickness: 60 μm), buffer layer 400 (thickness: 30 μm), composite positive electrode 220 (thickness: 90 μm), aluminum foil 210 (thickness: 6 μm), composite positive electrode 220 (thickness: 100 μm), buffer layer 400 (thickness: 40 μm), non-woven fabric-reinforced solid electrolyte membrane 100 (thickness: 70 μm), lithium indium alloy negative electrode material 320 (thickness: 40 μm), and copper foil 310 (thickness: 10 μm).
And both sides of the copper foil are made of lithium indium negative electrode materials.
The non-woven fabric reinforced solid electrolyte membrane comprises LPSO and PTFE-based non-woven fabric (with a gram weight of 10 g/m)2A porosity of 95%, a thickness of 50 μm and a tensile strength of 4500N/cm2) And polyethylene oxide (900000), the mass ratio of LPSO, PTFE-based nonwoven fabric, and polyethylene oxide being 94: 3: 3, the preparation method of the non-woven fabric reinforced solid electrolyte membrane comprises the following steps: firstly, grinding LPSO, polyethylene oxide and cyclohexane for 0.8h at 250rpm to obtain mixed slurry; then coating the mixed slurry and PTFE-based non-woven fabric on the surface of a base material so as to form a diaphragm layer on the surface of the base material, and blade-coating the diaphragm layer in an argon atmosphere to obtain a diaphragm sheet; the separator sheet was vacuum-dried at 80 degrees celsius for about 14 hours and then hot-rolled to obtain a non-woven fabric-reinforced solid electrolyte membrane.
The buffer layer comprises polydimethylsiloxane and LiPF6Polydimethylsiloxane and LiPF6The mass ratio of (A) to (B) is 5: 1.
the composite positive electrode includes: the carbon-coated elemental sulfur, LPSO, carbon black and PVDF4 are mixed, wherein the mass ratio of the carbon-coated elemental sulfur to the LPSO to the carbon black to the PVDF4 is 50: 45: 2.5: 2.5.
and pressing the negative electrode, the non-woven fabric reinforced solid electrolyte membrane, the buffer layer, the positive electrode, the buffer layer, the non-woven fabric reinforced solid electrolyte membrane and the negative electrode at 80 ℃ and 5MPa, sharing an aluminum foil to obtain the double-layer solid lithium battery, wherein in the rolling process, a high molecular compound in each substance serves as a binder, so that a lithium indium alloy negative electrode material in the negative electrode is bonded with one side of the non-woven fabric reinforced solid electrolyte membrane, the other side of the non-woven fabric reinforced solid electrolyte membrane is bonded with one side of the buffer layer, and the other side of the buffer layer is bonded with the composite positive electrode in the positive electrode. The double-layer battery sharing the aluminum foil has the advantages that the short circuit of the anode and the cathode does not occur in the assembling and using processes, the preparation success rate is high, the phenomenon that dendrites penetrate through the electrode is obviously reduced in the using process of the battery, the double-layer battery sharing the aluminum foil is very suitable for large-scale industrial production, and the double-layer battery sharing the aluminum foil has obvious commercial property.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (35)

1. A solid state lithium battery, comprising: a non-woven fabric reinforced solid electrolyte membrane, a positive electrode, a negative electrode, and a buffer layer, wherein the non-woven fabric reinforced solid electrolyte membrane comprises: a first solid sulfide electrolyte, a non-woven fabric, and a first binder,
in the non-woven fabric-reinforced solid electrolyte membrane, the mass ratio of the first solid sulfide electrolyte to the non-woven fabric, the first binder is 80 to 97: 0.01-20: 3-10;
the first adhesive is at least one of ethylene oxide polymer, ethylene polymer, vinylidene fluoride polymer, styrene polymer and butadiene polymer.
2. The lithium battery as claimed in claim 1, wherein the tensile strength of the non-woven fabric-reinforced solid electrolyte membrane is 100-10000N/cm2And the elongation is 0-50%.
3. The lithium battery according to claim 1, wherein the non-woven fabric is at least one of a PP-based non-woven fabric, a PE-based non-woven fabric, a PET-based non-woven fabric, a PAN-based non-woven fabric, a PTFE-based non-woven fabric, and a Celgard non-woven fabric.
4. The lithium battery of claim 1, wherein the nonwoven fabric has a grammage of 1-10g/m2The porosity is 50-95%, the thickness is 10-50 μm, and the tensile strength is 200-4500N/cm2。
5. The lithium battery of claim 1 wherein the first solid sulfide electrolyte is at least one selected from the group consisting of LPS, LPSCl, LGPS, LSPS, LPSO, LPS with a modification of Si, Ta, Hf, Sc dopant, LPSCl with a modification of Si, Ta, Hf, Sc dopant, LGPS with a modification of Si, Ta, Hf, Sc dopant, LSPS with a modification of Si, Ta, Hf, Sc dopant, and LPSO with a modification of Si, Ta, Hf, Sc dopant.
6. The lithium battery as claimed in claim 1, wherein the molecular weight of the first binder is 100000-1000000.
7. The lithium battery of claim 1, wherein the non-woven fabric reinforced solid electrolyte membrane further comprises a first lithium salt selected from the group consisting of LiTFSI, LiFSI, LiN (SO)2CF2CF3)2、LiCF3SO3、LiPF6、LiClO4、LiBF4、LiPO2F2At least one of LiBOB and LiODFB.
8. The lithium battery of claim 1, wherein the positive electrode comprises an aluminum foil and a composite positive electrode, the composite positive electrode comprising: the composite material comprises a positive electrode active material, a nano coating material, a second solid sulfide electrolyte, a first conductive material and a second adhesive, wherein the nano coating material is coated on the surface of the positive electrode active material.
9. The lithium battery according to claim 8, wherein a mass ratio of the positive electrode active material to the second solid sulfide electrolyte, the first conductive material, and the second binder in the composite positive electrode is 50 to 95: 10-45: 0-10: 0-20.
10. The lithium battery according to claim 8, wherein the positive active material is selected from the group consisting of lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganate, lithium cobalt phosphate, lithium manganese nickel oxide, lithium cobaltate, and LiTiS2、LiNiO2At least one of elemental sulfur and a mixture of sulfur and carbon.
11. The lithium battery of claim 8, wherein the nanocoating material is selected from Li3PO4，Al2O3，LiNbO3，LiAlO2，Li3BO3，Li2O-ZrO2、MgO、HfO2，Li2SiO3、B2O3、Li2O、Nb2O5、P2O5、SiO2、Sc2O3、TiO2、ZrO2At least one of (a).
12. The lithium battery of claim 8, wherein the second solid sulfide electrolyte is at least one selected from LPS, LPSCl, LGPS, LSPS, LPSO, and variants of LPS or LPSCl or LGPS or LSPS or LPSO with Si, Ta, Hf, Sc dopants.
13. The lithium battery of claim 8, wherein the first conductive material is at least one selected from Super P, VGCF, carbon nanotube, acetylene black, ketjen black, and conductive graphene.
14. The lithium battery according to claim 8, wherein the second binder is at least one selected from the group consisting of an ethylene-based polymer, a styrene-based polymer, and a butadiene-based polymer.
15. The lithium battery as claimed in claim 8, wherein the molecular weight of the second binder is 1000-1000000.
16. The lithium battery as claimed in claim 8, wherein the molecular weight of the second binder is 5000-300000.
17. The lithium battery of claim 1, wherein the negative electrode comprises a current collector and a negative electrode material, wherein the current collector is a copper foil or a nickel foil, and the negative electrode material is lithium or indium or a lithium-indium alloy or a composite negative electrode.
18. The lithium battery of claim 17, wherein the composite negative electrode comprises: a negative active material, a solid electrolyte, a second conductive material, and a third binder.
19. The lithium battery as claimed in claim 18, wherein a mass ratio of the negative active material to the solid electrolyte, the second conductive material, and the third binder in the composite negative electrode is 40 to 85: 15-60: 0-10: 0-20.
20. The lithium battery of claim 18 or 19, wherein the negative active material is graphite or graphite containing silicon/silicon oxide nanoparticles.
21. The lithium battery of claim 18 or 19, wherein the solid electrolyte is at least one of a third solid sulfide electrolyte and a solid polymer electrolyte.
22. The lithium battery of claim 21, wherein the third solid sulfide electrolyte is at least one selected from LPS, LPSCl, LGPS, LSPS, LPSO, and variants of LPS or LPSCl or LGPS or LSPS or LPSO with Si, Ta, Hf, Sc dopants.
23. The lithium battery of claim 18 or 19, wherein the second conductive material is at least one selected from Super P, VGCF, carbon nanotubes, acetylene black, ketjen black, conductive graphene.
24. The lithium battery according to claim 18 or 19, wherein the third binder is at least one selected from the group consisting of an ethylene oxide-based polymer, a vinyl-based polymer, a styrene-based polymer, and a butadiene-based polymer.
25. The lithium battery as claimed in claim 18 or 19, wherein the molecular weight of the third binder is 1000-1000000.
26. The lithium battery as claimed in claim 18 or 19, wherein the molecular weight of the third binder is 5000-300000.
27. The lithium battery of claim 1, wherein the buffer layer has a thickness of 5-50 μm.
28. The lithium battery of claim 1, wherein the buffer layer comprises a polymer and a lithium-containing compound, the polymer is at least one selected from the group consisting of poly (oxyethylene methacrylate), polysiloxane, and polydimethylsiloxane, and the lithium-containing compound is at least one selected from the group consisting of a second lithium salt, a nano-ceramic oxide, and a nano-ceramic sulfide.
29. The lithium battery of claim 28, wherein a mass ratio of the polymer to the lithium-containing compound is 50-95: 5-50.
30. The lithium battery of claim 28, wherein the second lithium salt is selected from the group consisting of LiTFSI, LiFSI, LiN (SO)2CF2CF3)2、LiCF3SO3、LiPF6、LiClO4、LiBF4、LiPO2F2At least one of LiBOB and LiODFB.
31. The lithium battery of claim 1, wherein the buffer layer is stable at a voltage of less than 5.0v, stable at-30-150 ℃, and has an ionic conductivity greater than 10 at room temperature-4S/cm。
32. A vehicle, characterized in that it comprises a solid-state lithium battery according to any one of claims 1 to 31.
33. A method of producing a nonwoven fabric-reinforced solid electrolyte membrane that is the nonwoven fabric-reinforced solid electrolyte membrane of any one of claims 1 to 31, comprising:
mixing and grinding a first solid sulfide electrolyte, a first adhesive and a first solvent to obtain mixed slurry;
coating the mixed slurry and non-woven fabric on the surface of a base material so as to form a diaphragm layer on the surface of the base material, and blade-coating the diaphragm layer under an inert gas atmosphere so as to obtain a diaphragm sheet;
and carrying out vacuum drying on the diaphragm sheet, and then carrying out hot rolling to obtain the non-woven fabric reinforced solid electrolyte membrane.
34. The method according to claim 33, wherein the first solid sulfide electrolyte is washed with a second solvent before the first solid sulfide electrolyte is mixed and ground with the first binder and the first solvent, and the washed first solid sulfide electrolyte is dried in a vacuum environment.
35. The method as claimed in claim 33, wherein the first solid sulfide electrolyte, the first binder and the first solvent are mixed and ground at 100-300rpm for 0.5-1 h.
CN201910063972.8A 2019-01-23 2019-01-23 Solid lithium battery, application thereof and method for preparing non-woven fabric reinforced solid electrolyte membrane Active CN109786817B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910063972.8A CN109786817B (en) 2019-01-23 2019-01-23 Solid lithium battery, application thereof and method for preparing non-woven fabric reinforced solid electrolyte membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910063972.8A CN109786817B (en) 2019-01-23 2019-01-23 Solid lithium battery, application thereof and method for preparing non-woven fabric reinforced solid electrolyte membrane

Publications (2)

Publication Number Publication Date
CN109786817A CN109786817A (en) 2019-05-21
CN109786817B true CN109786817B (en) 2021-09-21

Family

ID=66501179

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910063972.8A Active CN109786817B (en) 2019-01-23 2019-01-23 Solid lithium battery, application thereof and method for preparing non-woven fabric reinforced solid electrolyte membrane

Country Status (1)

Country Link
CN (1) CN109786817B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI738280B (en) 2019-04-12 2021-09-01 康那香企業股份有限公司 Secondary battery structure having windable flexible polymer matrix solid electrolyte and manufacturing method thereof
CN112310471B (en) * 2019-07-29 2024-03-22 宁波纳微新能源科技有限公司 Composite solid electrolyte membrane, preparation method thereof and all-solid battery
CN112909343A (en) * 2019-12-04 2021-06-04 中国科学院宁波材料技术与工程研究所 Fabric-reinforced ultrathin sulfide electrolyte sheet, and preparation method and application thereof
CN111435755B (en) * 2019-12-23 2023-02-21 蜂巢能源科技有限公司 Sulfide solid-state battery and preparation method thereof
CN111162309B (en) * 2020-01-15 2022-07-12 东南大学 Solid electrolyte-anode composite material and preparation and application methods thereof
CN111952597A (en) * 2020-07-02 2020-11-17 南方科技大学 Composite positive plate, preparation method thereof and solid-state battery
CN111916629B (en) * 2020-07-23 2022-05-24 蜂巢能源科技有限公司 Composite solid electrolyte diaphragm and preparation method and application thereof
CN112768626B (en) * 2021-01-25 2022-07-15 欣旺达电动汽车电池有限公司 Positive pole piece, preparation method thereof and solid-state battery
CN114005982B (en) * 2021-10-09 2023-03-17 北京科技大学 In-situ functional coated cathode material, preparation method thereof and all-solid-state lithium battery
CN114639869A (en) * 2022-03-25 2022-06-17 厦门海辰新能源科技有限公司 Solid electrolyte, preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105098227A (en) * 2015-08-22 2015-11-25 哈尔滨工业大学 All-solid-state lithium ion battery and preparation method thereof
CN105280884A (en) * 2014-05-26 2016-01-27 现代自动车株式会社 Method for manufacturing all solid electrode having solid electrolyte concentration gradient
CN105470564A (en) * 2016-01-22 2016-04-06 山东鸿正电池材料科技有限公司 Solid electrolyte membrane, preparation method of solid electrolyte membrane and lithium ion battery
CN106654362A (en) * 2016-12-07 2017-05-10 珠海光宇电池有限公司 Composite solid electrolyte membrane, preparation method and lithium-ion battery
CN106784966A (en) * 2016-12-07 2017-05-31 中国科学院化学研究所 One class low interfacial resistance, the preparation method and application of high mechanical properties all-solid-state battery
CN108232293A (en) * 2018-01-03 2018-06-29 清陶（昆山）能源发展有限公司 A kind of Organic-inorganic composite solid electrolyte and preparation method and its application in solid state lithium battery
CN108598563A (en) * 2018-04-27 2018-09-28 溧阳天目先导电池材料科技有限公司 A kind of aqueous solid electrolyte membrane and preparation method thereof and secondary cell
CN108832060A (en) * 2018-05-31 2018-11-16 中国科学院物理研究所 Composite diaphragm and its preparation method and application for lithium battery
WO2018212568A1 (en) * 2017-05-15 2018-11-22 주식회사 엘지화학 Method for manufacturing solid electrolyte membrane for solid-state battery and solid electrolyte membrane manufactured by same method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105280884A (en) * 2014-05-26 2016-01-27 现代自动车株式会社 Method for manufacturing all solid electrode having solid electrolyte concentration gradient
CN105098227A (en) * 2015-08-22 2015-11-25 哈尔滨工业大学 All-solid-state lithium ion battery and preparation method thereof
CN105470564A (en) * 2016-01-22 2016-04-06 山东鸿正电池材料科技有限公司 Solid electrolyte membrane, preparation method of solid electrolyte membrane and lithium ion battery
CN106654362A (en) * 2016-12-07 2017-05-10 珠海光宇电池有限公司 Composite solid electrolyte membrane, preparation method and lithium-ion battery
CN106784966A (en) * 2016-12-07 2017-05-31 中国科学院化学研究所 One class low interfacial resistance, the preparation method and application of high mechanical properties all-solid-state battery
WO2018212568A1 (en) * 2017-05-15 2018-11-22 주식회사 엘지화학 Method for manufacturing solid electrolyte membrane for solid-state battery and solid electrolyte membrane manufactured by same method
CN108232293A (en) * 2018-01-03 2018-06-29 清陶（昆山）能源发展有限公司 A kind of Organic-inorganic composite solid electrolyte and preparation method and its application in solid state lithium battery
CN108598563A (en) * 2018-04-27 2018-09-28 溧阳天目先导电池材料科技有限公司 A kind of aqueous solid electrolyte membrane and preparation method thereof and secondary cell
CN108832060A (en) * 2018-05-31 2018-11-16 中国科学院物理研究所 Composite diaphragm and its preparation method and application for lithium battery

Also Published As

Publication number Publication date
CN109786817A (en) 2019-05-21

Similar Documents

Publication Publication Date Title
CN109786817B (en) Solid lithium battery, application thereof and method for preparing non-woven fabric reinforced solid electrolyte membrane
US9843045B2 (en) Negative electrode active material and method for producing the same
CN104425825B (en) Lithium ion battery electrode structure and preparation method thereof
CN111816856B (en) Composite material, preparation method thereof and negative electrode
KR20130094366A (en) Negative active material and lithium battery containing the material
US20150221952A1 (en) Positive electrode for lithium air battery and lithium air battery including the same
CN114556611A (en) Negative electrode and secondary battery comprising same
US20180277847A1 (en) Compositions and methods for passivation of electrode binders
CN114242942B (en) Composite buffer layer with stable anode interface and solid-state lithium metal battery thereof
TWI785058B (en) Sulfur-carbon material composite, positive electrode material for lithium-sulfur secondary battery, and lithium-sulfur secondary battery
US11394054B2 (en) Polymer microspheres as binders for composite electrolytes
CN114068857A (en) Preparation method and application of electrode slice
WO2024113407A1 (en) Positive electrode sheet, preparation method therefor, and sodium-ion battery
CN113273014A (en) Lithium secondary battery and method for manufacturing same
WO2023231738A1 (en) Solid-state electrode unit, preparation method, and solid-state battery and system comprising same
CN109417167A (en) Cladding lithium titanate for lithium ion battery
US20220021079A1 (en) Polymer microspheres as binders for composite electrolytes
Si et al. Silicon–carbon composite dispersed in a carbon paper substrate for solid polymer lithium-ion batteries
CN116670850A (en) Negative electrode and secondary battery including the same
JP2023520194A (en) Negative electrode and secondary battery containing the same
CN109690839B (en) Flexible electrode-separator element and method for the production thereof
WO2017177960A1 (en) Electrolyte solution, battery, and battery pack
US20200295333A1 (en) Separators for electrochemical cells and methods of making the same
CN116014225A (en) Sodium ion battery
CN114497440B (en) Negative plate and battery comprising same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: No.8899 Xincheng Avenue, Jintan District, Changzhou City, Jiangsu Province

Patentee after: SVOLT Energy Technology Co.,Ltd.

Address before: 213200 168 Huacheng Road, Jintan District, Changzhou, Jiangsu

Patentee before: SVOLT Energy Technology Co.,Ltd.