Search

CN-122000423-A - All-solid-state battery comprising double-layer solid electrolyte and method for manufacturing same

CN122000423ACN 122000423 ACN122000423 ACN 122000423ACN-122000423-A

Abstract

The present invention provides an all-solid battery including a double-layered solid electrolyte capable of improving the robustness of an electrolyte layer while suppressing a thermal runaway phenomenon and exhibiting excellent electrochemical characteristics, and a method of manufacturing the same. The all-solid battery includes a negative electrode, a first solid electrolyte layer on the negative electrode, a second solid electrolyte layer on the first solid electrolyte layer, and a positive electrode on the second solid electrolyte layer. The first solid electrolyte layer comprises an inorganic flame retardant and the second solid electrolyte layer comprises an endothermic flame retardant.

Inventors

  • Jin Minxuan
  • YIN RUMIN
  • CUI RONGSHUO
  • Nan Rongzhen

Assignees

  • 现代自动车株式会社
  • 起亚株式会社

Dates

Publication Date
20260508
Application Date
20250526
Priority Date
20241104

Claims (20)

  1. 1. An all-solid battery comprising: A negative electrode; A first solid electrolyte layer on the anode; a second solid electrolyte layer on the first solid electrolyte layer, and A positive electrode on the second solid electrolyte layer, Wherein the first solid electrolyte layer contains an inorganic flame retardant, and Wherein the second solid electrolyte layer comprises an endothermic flame retardant.
  2. 2. The all-solid battery according to claim 1, wherein the inorganic flame retardant comprises at least one selected from LLZO, LATP, siO 2 、ZnO、SnO 2 、Mn 3 O 4 、Sn 2 P 2 O 7 , alumina, magnesia, zeolite, zirconium compound, calcium salt, and boron compound.
  3. 3. The all-solid battery according to claim 1, wherein the content of the inorganic flame retardant contained in the first solid electrolyte layer is in the range of 20wt% to 50wt%, based on the weight of the solid electrolyte contained in the first solid electrolyte layer.
  4. 4. The all-solid battery according to claim 1, wherein the endothermic flame retardant comprises at least one selected from Mg(OH) 2 、Al(OH) 3 、Sb 2 O 3 、H 3 BO 3 、Fe(OH) 3 、CaCO 3 、Ca(OH) 2 、Zn(OH) 2 、NaOH、 calcium magnesium hydroxide, hydrotalcite, boehmite, talc, dawsonite, calcium sulfate hydrate, and magnesium sulfate hydrate.
  5. 5. The all-solid battery according to claim 1, wherein the content of the second solid electrolyte layer containing the endothermic flame retardant is in the range of 5wt% to 20wt%, based on the weight of the solid electrolyte contained in the second solid electrolyte layer.
  6. 6. The all-solid battery according to claim 1, wherein a ratio of a thickness of the first solid electrolyte layer to a thickness of the second solid electrolyte layer is 1:9 to 9:1.
  7. 7. The all-solid battery according to claim 1, wherein a sum of a thickness of the first solid electrolyte layer and a thickness of the second solid electrolyte layer is 10 μm to 120 μm.
  8. 8. The all-solid battery according to claim 1, wherein the first solid electrolyte layer and the second solid electrolyte layer each further comprise a binder.
  9. 9. The all-solid battery according to claim 8, wherein the content of the binder is in the range of 0.5wt% to 5wt%, based on the weight of the respective solid electrolytes of the first solid electrolyte layer and the second solid electrolyte layer.
  10. 10. The all-solid battery according to claim 8, wherein the binder comprises at least one selected from the group consisting of polybutadiene rubber BR, styrene-butadiene rubber SBR, nitrile-butadiene rubber NBR, polyimide PI, polyvinylidene fluoride PVDF, and ethylene-propylene-diene monomer EPDM.
  11. 11. A method of manufacturing an all-solid battery, the method comprising the steps of: the all-solid battery is manufactured in which a negative electrode, a first solid electrolyte layer, a second solid electrolyte layer, and a positive electrode are sequentially stacked, Wherein the first solid electrolyte layer contains an inorganic flame retardant, and Wherein the second solid electrolyte layer comprises an endothermic flame retardant.
  12. 12. The method of claim 11, wherein the step of manufacturing the all-solid-state battery comprises the steps of: manufacturing a negative electrode assembly by sequentially stacking the negative electrode, the first solid electrolyte layer, and the second solid electrolyte layer, and The anode assembly and the cathode are stacked such that the second solid electrolyte layer faces the cathode.
  13. 13. The method of claim 12, wherein the negative electrode assembly is manufactured in a wet-on-wet or wet-on-dry solution.
  14. 14. The method of claim 11, wherein the step of manufacturing the all-solid-state battery comprises the steps of: Manufacturing a positive electrode assembly by stacking the positive electrode, the second solid electrolyte layer, and the first solid electrolyte layer in this order, and The positive electrode assembly and the negative electrode are stacked such that the first solid electrolyte layer faces the negative electrode.
  15. 15. The method of claim 14, wherein the positive electrode assembly is manufactured in a wet-on-wet or wet-on-dry scheme.
  16. 16. The method of claim 11, wherein the step of manufacturing the all-solid-state battery comprises the steps of: fabricating the anode assembly including the anode and the first solid electrolyte layer; Manufacturing the positive electrode assembly including the positive electrode and the second solid electrolyte layer, and The anode assembly and the cathode assembly are stacked such that the first solid electrolyte layer and the second solid electrolyte layer face each other.
  17. 17. The method of claim 16, wherein the negative electrode assembly or the positive electrode assembly are each manufactured in a wet-on-wet or wet-on-dry scheme.
  18. 18. An all-solid battery comprising: A negative electrode; A first solid electrolyte layer on the anode; a second solid electrolyte layer on the first solid electrolyte layer, and A positive electrode on the second solid electrolyte layer, Wherein the first solid electrolyte layer comprises at least one component selected from LLZO, LATP, siO 2 、ZnO、SnO 2 、Mn 3 O 4 、Sn 2 P 2 O 7 , alumina, magnesia, zeolite, zirconium compound, calcium salt, and boron compound, and Wherein the second solid electrolyte layer comprises at least one component selected from Mg(OH) 2 、Al(OH) 3 、Sb 2 O 3 、H 3 BO 3 、Fe(OH) 3 、CaCO 3 、Ca(OH) 2 、Zn(OH) 2 、NaOH、 calcium magnesium hydroxide, hydrotalcite, boehmite, talc, dawsonite, calcium sulfate hydrate, and magnesium sulfate hydrate.
  19. 19. The all-solid battery of claim 18, wherein the first solid electrolyte layer comprises at least one component in an amount ranging from 20wt% to 50wt%, based on the weight of solid electrolyte contained in the first solid electrolyte layer.
  20. 20. The all-solid battery according to claim 18, wherein the second solid electrolyte layer contains at least one component in an amount ranging from 5wt% to 20wt%, based on the weight of the solid electrolyte contained in the second solid electrolyte layer.

Description

All-solid-state battery comprising double-layer solid electrolyte and method for manufacturing same Cross Reference to Related Applications The present application claims priority from korean patent application No. 10-2024-0154681 filed on the korean intellectual property office on month 4 of 2024, the entire contents of which are incorporated herein by reference. Technical Field The present invention relates to an all-solid battery including a double-layered solid electrolyte capable of improving the robustness of the electrolyte layer while suppressing a thermal runaway phenomenon, and a method of manufacturing the same. Background Lithium secondary batteries have been widely used in various fields such as electric vehicles and portable electronic devices, but also have some safety problems. Specifically, in order to increase the energy density, a positive electrode material having a higher nickel (Ni) content is mainly used, but this lowers the pyrolysis starting temperature, increases the amount of heat generation, and thus increases the risk of thermal runaway phenomenon. In addition, in order to increase the theoretical capacity, a silicon (Si) anode is also used. The silicon negative electrode has severe volume expansion in the charging/discharging process, and lithium metal can be separated out after long-time charging/discharging, so that internal short circuit of the battery is caused, and thermal runaway phenomenon is caused. Accordingly, an all-solid-state battery has received significant attention as a next-generation energy storage device because it employs a solid electrolyte different from existing lithium ion batteries, and can reduce leakage of the electrolyte or risk of fire. However, all solid-state batteries also have safety problems such as thermal runaway phenomenon. In particular, it is difficult to maintain thermal stability and mechanical stability between the positive electrode and the negative electrode due to the multi-layered structure characteristics of the all-solid battery. Therefore, there is a need to develop an all-solid-state battery capable of maintaining energy density and performance while securing thermal stability and mechanical stability. Disclosure of Invention The present invention aims to solve the above-mentioned problems occurring in the prior art while fully retaining the advantages achieved by the prior art. An aspect of the present invention relates to an all-solid battery including a double-layered solid electrolyte capable of improving the robustness of an electrolyte layer while suppressing a thermal runaway phenomenon, and a method of manufacturing the same. More specifically, the present invention aims to improve the robustness of an electrolyte layer by a first solid electrolyte layer containing an inorganic flame retardant, and to reduce the heating start temperature by a second solid electrolyte layer containing an endothermic flame retardant, thereby suppressing the thermal runaway phenomenon. The technical problems to be solved by the present invention are not limited to the above-described problems, and any other technical problems not mentioned herein will be clearly understood by those skilled in the art to which the present invention pertains from the following description. According to one aspect of the present invention, there is provided an all-solid battery including a double-layered solid electrolyte and a method of manufacturing the same. In more detail, (1) the present invention provides an all-solid battery comprising a negative electrode, a first solid electrolyte layer on the negative electrode, a second solid electrolyte layer on the first solid electrolyte layer, and a positive electrode on the second solid electrolyte layer. The first solid electrolyte layer comprises an inorganic flame retardant and the second solid electrolyte layer comprises an endothermic flame retardant. (2) The present invention provides an all-solid battery as in (1), wherein the inorganic flame retardant comprises at least one selected from LLZO, LATP, siO 2、ZnO、SnO2、Mn3O4、Sn2P2O7, alumina, magnesia, zeolite, zirconium compound, calcium salt and boron compound. (3) The present invention provides an all-solid battery as in (1) or (2), wherein the first solid electrolyte layer contains an inorganic flame retardant in an amount in the range of 20 to 50wt% based on the weight of the solid electrolyte contained in the first solid electrolyte layer. (4) The present invention provides an all-solid battery according to any one of (1) to (3), wherein the endothermic flame retardant comprises at least one selected from Mg(OH)2、Al(OH)3、Sb2O3、H3BO3、Fe(OH)3、CaCO3、Ca(OH)2、Zn(OH)2、NaOH、 calc magnesium hydroxide, hydrotalcite, boehmite, talc, dawsonite, calcium sulfate hydrate and magnesium sulfate hydrate. (5) The present invention provides an all-solid battery according to any one of (1) to (4), wherein the second solid electrolyte layer contains an endothermic flame re