Preparation method of implantable lithium ion solid-state battery

Abstract

The invention belongs to the field of solid-state lithium metal batteries, and particularly discloses a preparation method of an implantable lithium-ion solid-state battery, which comprises the following steps: (1) wetting an interface between a positive electrode and a solid-state electrolyte and an interface between a negative electrode and the solid-state electrolyte by using a small amount of aqueous electrolyte in a glove box in an argon atmosphere; and (2) then selecting at least one of a graphite negative electrode, a hard carbon negative electrode or a silicon carbon negative electrode, and assembling the button cell. The lithium ion solid-state battery based on the solid electrolyte and the aqueous electrolyte has the advantages of high energy density, high safety, high biocompatibility and low self-discharge rate, and can meet the requirements of implantable equipment on long cycle life and high safety.

Description

Technical Field

[0001] The present invention belongs to the field of lithium ion solid-state batteries, and in particular relates to a method for preparing an implantable lithium ion solid-state battery. Background Art

[0002] Implantable medical devices, such as pacemakers, neurostimulators, and drug delivery systems, have revolutionized modern healthcare by providing long-term therapeutic and diagnostic solutions. However, developing a safe, reliable, and long-lasting power source remains a key challenge for these devices. Conventional lithium-ion batteries using liquid electrolytes present safety risks due to leakage, flammability, and lithium dendrite formation, which can lead to short circuits and device failure. To address these limitations, solid-state lithium batteries have emerged as a promising alternative for implantable applications.

[0003] Solid-state batteries replace traditional liquid electrolytes such as ceramics, polymers or composites with solid electrolytes. This shift offers several key advantages, including enhanced safety, higher energy density, longer cycle life and better biocompatibility. The elimination of flammable organic solvents greatly reduces the risk of thermal runaway, ensuring safer operation in the human body. In addition, solid-state electrolytes can inhibit lithium dendrite growth, thereby extending battery life and reliability, which is critical for the long-term functionality of implantable medical devices.

[0004] Another significant advantage of solid-state batteries is their compatibility with flexible and miniaturized designs. Solid-state electrolytes enable the development of thin films and micro-batteries that conform to the human anatomy, allowing for more seamless integration into biomedical implants. In addition, recent advances in aqueous electrolytes and solid-state electrolytes have further improved the biocompatibility of solid-state batteries, minimizing potential toxic effects in the event of leakage. Summary of the invention

[0005] The purpose of the present invention is to broaden the application scenarios of solid-state batteries and prepare implantable solid-state batteries with high energy density, high safety and high biocompatibility.

[0006] To this end, the present invention provides a method for preparing an implantable lithium-ion solid-state battery, comprising:

[0007] In a glove box under an argon atmosphere, a small amount of aqueous electrolyte is used to wet the interface between the positive electrode and the solid electrolyte and the interface between the negative electrode and the solid electrolyte; the solid electrolyte is an inorganic solid electrolyte, preferably selected from garnet-type solid electrolyte, LISICON-type solid electrolyte, NASICON-type solid electrolyte, LiTa 2 PO 8 At least one of a type solid electrolyte, a halide electrolyte and a perovskite solid electrolyte.

[0008] Furthermore, the NASICON solid electrolyte is Li (1+x) Al x Ti (2-x) P 3 O 12 or / and Li (1+y) Al y Ge (2-y) P 3 O 12 , 0≤x≤2, 0≤y≤2; the perovskite solid electrolyte is Li 3z La 2 / 3-z TiO 3 , 0≤z≤2 / 3; the LISICON type solid electrolyte is Li 14 Zn(GeO 4 ) 4 ; The garnet-type solid electrolyte is Li 7-m La 3 Zr 2-m M m O 12 (M=Ta, Nb; 0≤m≤2), Li 7-2n La 3 Zr 2-n NnO 12 (N=W, Mo; 0≤n≤2), Li 7-3d D d La 3 Zr 2 O 12 (D=Ga, Al; 0≤d≤7 / 3), the LiTa 2 PO 8 The solid electrolyte is Li a Ta b M c P d O e (M = one or more elements selected from Nb, Zr, Ga, Sn, Hf, Bi, W, B, F, Mo, Si, Al and Ge; 0.5 < a < 2.0, 1.0 < b ≤ 2.0, 0 < c < 0.5, 0.5 < d < 1.0, 5.0 < e ≤ 8.0); the halide solid electrolyte is Li 3 InCl 6 、LiYCl 6 , Li 4 I 6 , Li 3 Yb 6 , Li 3 InBr 6 , Li 4 GeCl 6 , Li 3InI 6 , Li 3 YI 6 , Li 7 Ge 3 Cl 12 , Li 5 InCl 12 One or a mixture of two or more materials.

[0009] Furthermore, the aqueous electrolyte solute is one or more of lithium bis(trifluoromethanesulfonate)imide, lithium bis(fluorosulfonyl)imide, lithium perchlorate, lithium hexafluorophosphate, and lithium tetrafluoroborate.

[0010] Furthermore, the aqueous electrolyte additive is at least one of urea, dimethyl isosorbide, and trehalose, and the solvent is water.

[0011] Furthermore, the concentration of the aqueous electrolyte additive is 0.01 to 80 wt %, preferably 1 to 20 wt %.

[0012] Furthermore, the solute concentration of the aqueous electrolyte is 0.01 to 80 wt%, preferably 1 to 20 wt%.

[0013] Furthermore, the amount of the aqueous electrolyte added per unit area is 0.1 to 20 μL / cm 2 .

[0014] Furthermore, the negative electrode is at least one of a graphite negative electrode, a hard carbon negative electrode, and a silicon-carbon negative electrode.

[0015] Furthermore, the implantable lithium-ion solid-state battery includes: a positive electrode, a negative electrode, a solid electrolyte, an interface between the positive electrode and the solid electrolyte, and an aqueous electrolyte added to the interface between the negative electrode and the solid electrolyte.

[0016] Furthermore, the positive electrode is LiFePO 4 、LiCoO 2 、LiNi b Co c Mn 1-b-c O 2 (0≤b≤1,0≤c≤1), LiNi 0.8 Co 0.15 Al 0.05 、LiMn 2 O 4 , lithium-rich phase aLi 2 MnO 3·(1-a) LiMO 2 At least one of (M=Mn, Ni or Co, 0≤a≤1).

[0017] The advantages of the present invention are:

[0018] This solid-state battery has the advantages of high energy density, high safety, high biocompatibility and low self-discharge rate, and can meet the requirements of long cycle life and high safety of implantable devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a preparation flow chart of the implantable lithium-ion solid-state battery.

Claims

1. A method for preparing an implantable lithium-ion solid-state battery, characterized in that: include: In a glove box under an argon atmosphere, a small amount of aqueous electrolyte is used to wet the interface between the positive electrode and the solid electrolyte and the interface between the negative electrode and the solid electrolyte respectively; The solid electrolyte is an inorganic solid electrolyte, preferably selected from at least one of a garnet-type solid electrolyte, a LISICON-type solid electrolyte, a NASICON-type solid electrolyte, a LiTa2PO8-type solid electrolyte, a halide electrolyte and a perovskite-type solid electrolyte.

2. A preparation method according to claim 1, characterized in that: The NASICON solid electrolyte is Li (1+x) Al x Ti (2-x) P3O 12 or / and Li (1+y) Al y Ge (2-y) P3O 12 , 0≤x≤2, 0≤y≤2; the perovskite solid electrolyte is Li 3z La 2 / 3-z TiO3, 0≤z≤2 / 3; the LISICON type solid electrolyte is Li 14 Zn(GeO4)4; the garnet-type solid electrolyte is Li 7-m LqCy 2-m M m O 12 (M=Ta, Nb; 0≤m≤2), Li 7-2n LqCy 2-n NnO 12 (N=W, Mo; 0≤n≤2), Li 7-3d D d La3Zr2O 12 (D = Ga, Al; 0 ≤ d ≤ 7 / 3), the LiTa2PO8 type solid electrolyte is Li a Ta b M c P d O e (M=one or more elements selected from Nb, Zr, Ga, Sn, Hf, Bi, W, B, F, Mo, Si, Al and Ge; 0.5<a<2.0, 1.0<b≤2.0, 0<c<0.5, 0.5<d<1.0, 5.0<e≤8.0); the halide solid electrolyte is Li3InCl6, LiYCl6, Li4GeI6, Li3YBr6, Li3InBr6, Li4GeCl6, Li3InI6, Li3YI6, Li7Ge3Cl 12 、Li5InCl 12 One or a mixture of two or more materials.

3. The preparation method according to claim 1 or 2, characterized in that: The aqueous electrolyte solute is one or more of lithium bis(trifluoromethanesulfonate)imide, lithium bis(fluorosulfonyl)imide, lithium perchlorate, lithium hexafluorophosphate, and lithium tetrafluoroborate.

4. The preparation method according to any one of claims 1 to 3, characterized in that The aqueous electrolyte additive is at least one of urea, dimethyl isosorbide and trehalose, and the solvent is water.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The concentration of the aqueous electrolyte additive is 0.01 to 80 wt %, preferably 1 to 20 wt %.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The solute concentration of the aqueous electrolyte is 0.01 to 80 wt %, preferably 1 to 20 wt %.

7. The preparation method according to any one of claims 1 to 6, characterized in that The amount of the aqueous electrolyte added per unit area is 0.1 to 20 μL / cm 2 .

8. The preparation method according to any one of claims 1 to 7, characterized in that: The negative electrode is at least one of a graphite negative electrode, a hard carbon negative electrode, and a silicon-carbon negative electrode.

9. A lithium-ion solid-state battery, characterized in that: include: Aqueous electrolyte added to the positive electrode, negative electrode, solid electrolyte, interface between the positive electrode and the solid electrolyte, and interface between the negative electrode and the solid electrolyte.

10. The implantable lithium-ion solid-state battery according to claim 9, characterized in that: The positive electrode is LiFePO4, LiCoO2, LiNi b Co c Mn 1-b-c O2(0≤b≤1,0≤c≤1), LiNi 0.8 Co 0.15 Al 0.05 , LiMn2O4, lithium-rich phase aLi2MnO 3·(1-a) At least one of LiMO2 (M = Mn, Ni or Co, 0≤a≤1).

Images