WO2022233023A1 - 固态电解质材料、其制备方法及使用该固态电解质材料的极片、电池芯 - Google Patents

固态电解质材料、其制备方法及使用该固态电解质材料的极片、电池芯 Download PDF

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WO2022233023A1
WO2022233023A1 PCT/CN2021/092091 CN2021092091W WO2022233023A1 WO 2022233023 A1 WO2022233023 A1 WO 2022233023A1 CN 2021092091 W CN2021092091 W CN 2021092091W WO 2022233023 A1 WO2022233023 A1 WO 2022233023A1
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solid electrolyte
pole piece
equal
active layer
electrolyte material
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PCT/CN2021/092091
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English (en)
French (fr)
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黄国进
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迪吉亚节能科技股份有限公司
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Priority to PCT/CN2021/092091 priority Critical patent/WO2022233023A1/zh
Publication of WO2022233023A1 publication Critical patent/WO2022233023A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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

Definitions

  • the present invention relates to a solid electrolyte material, in particular to an amorphous or microcrystalline solid electrolyte ion conductor material, a preparation method thereof, and a pole piece and a battery core using the solid electrolyte material.
  • the inventor has developed a design that is easy to assemble, can avoid the above shortcomings, is easy to install, and has the advantages of low cost, in order to take into account considerations such as flexibility and economy, and thus the invention is born.
  • the technical problem to be solved by the present invention is how to prepare a solid electrolyte material with high thermal stability, how to use the aforementioned solid electrolyte material with high thermal stability to prepare a positive electrode piece, a negative electrode piece, and how to use the aforementioned positive electrode
  • the battery cell is prepared by using the anode and cathode, so that the positive electrode, the negative electrode and the solid electrolyte material are highly bonded, so as to reduce the solid-state interface impedance of the battery cell and thereby increase the solid-state ionic conductivity.
  • the present invention provides a solid electrolyte material, the composition of which is [(Li 2 S) x (P 2 S 5 ) (100-x) ] y [z] (100- y) , wherein 70 ⁇ x ⁇ 80, 70 ⁇ y ⁇ 95, z is at least one of LiCl, LiBr and LiI, wherein the solid electrolyte material is amorphous or microcrystalline.
  • the present invention also provides a method for preparing a solid electrolyte material, comprising the following steps: mixing [(Li 2 S) x (P 2 S 5 ) (100-x) ] y [z] (100-y) into a Precursor mixture, wherein 70 ⁇ x ⁇ 80, 70 ⁇ y ⁇ 95, z is at least one of LiCl, LiBr and LiI; perform a mechanical alloying process on the precursor mixture in an inert gas environment to form a mechanical alloy Precursor; and subjecting the mechanical alloy post-precursor to a heat treatment in an environment of inert gas to form an amorphous or microcrystalline solid electrolyte material, wherein a temperature of the heat treatment is greater than or equal to 200° C. and less than or equal to At 500°C, the heat treatment time is greater than or equal to two hours and less than or equal to seven hours.
  • the present invention also provides a pole piece using a solid electrolyte material, comprising: a carrier plate, a polar active layer and a solid electrolyte layer.
  • the polar active layer is formed on the carrier plate; the solid electrolyte layer is formed on an outer surface of the polar active layer; and the materials constituting the solid electrolyte layer include the aforementioned solid electrolyte materials.
  • the polar active layer is a positive active layer
  • the pole piece is a positive pole piece
  • the polar active layer is a negative electrode active layer
  • the pole piece is a negative pole piece
  • the present invention also provides a method for preparing a pole piece using a solid electrolyte material, comprising the following steps: grinding the aforementioned solid electrolyte material into powder; uniformly mixing and stirring the powdered solid electrolyte material and a binder to form a Solid electrolyte slurry; coating solid electrolyte slurry on an outer surface of a polar active layer in an environment with a dew point of -50°C to form a slurry-coated pole piece; and at a temperature greater than or equal to - Under a negative pressure environment of 2000Pa and less than or equal to -500Pa, a negative pressure heating process is performed on the slurry-coated pole piece to dry the solid electrolyte slurry to form a pole piece including a solid electrolyte layer and a polar active layer.
  • a temperature of the negative pressure heating process is greater than or equal to 100°C and less than or equal to 150°C, and a time of the negative pressure heating process is greater than or equal to 10 minutes.
  • a thickness of the solid electrolyte slurry coated on the outer surface of the polar active layer is greater than or equal to 10 ⁇ m and less than or equal to 100 ⁇ m.
  • the present invention also provides a battery core using a solid electrolyte material, comprising: the aforementioned negative electrode sheet and the aforementioned positive electrode sheet.
  • the solid electrolyte layer of the positive pole piece is combined with the solid electrolyte layer of the negative pole piece.
  • the present invention also provides a method for preparing a battery core using a solid electrolyte material, comprising the following steps: stacking the aforementioned negative pole piece and the aforementioned positive pole piece into a battery core, wherein the solid electrolyte layer of the positive pole piece and the negative pole The solid electrolyte layer of the sheet is adjacent; and a hot pressing process is performed on the battery core, wherein a pressure of the hot pressing process is greater than or equal to 50MPa and less than or equal to 250MPa, and a temperature of the hot pressing process is greater than or equal to 100 °C, and less than or It is equal to 200°C, and the time of the hot pressing process is greater than or equal to 1 minute.
  • a pressure of the hot pressing process is greater than or equal to 50MPa and less than or equal to 250MPa
  • a temperature of the hot pressing process is greater than or equal to 100 °C, and less than or It is equal to 200°C
  • the time of the hot pressing process is greater than or equal to 1 minute.
  • it also includes a solid electrolyte sheet, which is located between the solid electrolyte layer of the positive electrode and the solid electrolyte layer of the negative electrode, and the solid electrolyte sheet is respectively connected to the solid electrolyte layer of the positive electrode and the negative electrode.
  • the solid electrolyte layer of the sheet is combined, wherein the material constituting the solid electrolyte sheet includes the aforementioned solid electrolyte material.
  • FIG. 1 is a schematic cross-sectional view of a specific embodiment of a pole piece using a solid electrolyte material according to the present invention
  • FIG. 2 is a schematic cross-sectional view of a step of a method for preparing a pole piece using a solid electrolyte material according to the present invention
  • FIG. 3 is a schematic cross-sectional view of a step of a method for preparing a solid electrolyte sheet using a solid electrolyte material according to the present invention
  • FIG. 4 is a schematic cross-sectional view of a specific embodiment of a battery cell using a solid electrolyte material according to the present invention.
  • FIG. 5 is a schematic cross-sectional view of another specific embodiment of a battery cell using a solid electrolyte material according to the present invention.
  • the present invention provides a solid electrolyte material, the composition of which is: [(Li 2 S) x (P 2 S 5 ) (100-x) ] y [z] (100-y) , wherein 70 ⁇ x ⁇ 80, 70 ⁇ y ⁇ 95, z is at least one of LiCl (lithium chloride), LiBr (lithium bromide), and LiI (lithium iodide).
  • the present invention provides a method for preparing a solid electrolyte material, comprising the following steps: mixing [(Li 2 S) x (P 2 S 5 ) (100-x) ] y [z] (100-y) into a precursor mixture, wherein 70 ⁇ x ⁇ 80, 70 ⁇ y ⁇ 95, z is at least one of LiCl, LiBr and LiI; perform a mechanical alloying process on the precursor mixture in an inert gas environment to form a mechanical alloy Precursor, wherein the aforementioned mechanical alloying process can enable the precursor mixture to form a mechanically alloyed post-precursor in a relatively stable state; and a heat treatment is performed on the above-mentioned mechanically alloyed post-precursor in an environment of inert gas to form a solid electrolyte material, wherein the solid state
  • the electrolyte material is an amorphous or microcrystalline solid electrolyte ion conductor.
  • the aforementioned inert gas can be helium, neon, argon, krypton, xenon, or a combination of the aforementioned gases.
  • a temperature of the aforementioned heat treatment is greater than or equal to 200°C and less than or equal to 500°C.
  • a time period of the aforementioned heat treatment is greater than or equal to two hours and less than or equal to seven hours.
  • the aforementioned mechanical alloying process may use a high-energy ball mill or a high-energy mill for mechanical alloying.
  • the temperature of the aforementioned heat treatment is 230° C.
  • the duration of the aforementioned heat treatment is six hours.
  • the aforementioned inert gas is argon.
  • FIG. 1 is a schematic cross-sectional view of a specific embodiment of a pole piece using a solid electrolyte material according to the present invention.
  • the present invention provides a pole piece 6 using a solid electrolyte material, comprising a carrier plate 9 , a polar active layer 2 and a solid electrolyte layer 1 .
  • the polar active layer 2 is formed on the carrier plate 9 .
  • the solid electrolyte layer 1 is formed on an outer surface 22 of the polar active layer 2 .
  • the polar active layer 2 can be a positive active layer 20 or a negative active layer 21 ; and the carrier 9 can be a positive carrier 4 or a negative carrier 5 .
  • the carrier plate 9 is the positive electrode carrier plate 4
  • the pole piece 6 is a positive electrode pole piece 60
  • the materials constituting the positive electrode active layer 20 include LiCoO 2 (lithium cobalt oxide), LiFePO At least one of 4 (lithium iron phosphate), lithium nickel cobalt manganate (NCM) and lithium nickel cobalt aluminate (NCA).
  • the carrier plate 9 is the negative electrode carrier plate 5
  • the pole piece 6 is a negative electrode pole piece 61
  • the materials constituting the negative electrode active layer 21 include graphite, hard carbon, soft carbon, Li At least one of 4 Ti 5 O 12 , TiNb 2 O 7 and SiC (silicon carbide).
  • the present invention provides a method for preparing a pole piece using a solid electrolyte material, comprising the following steps (please refer to FIG.
  • the polar active layer 2 is formed on the carrier plate 9; the aforementioned solid electrolyte material is ground into powder; the powdered solid electrolyte material and a binder are uniformly mixed and stirred to form a solid electrolyte slurry 3, wherein , the proportion of the binder in the solid electrolyte slurry 3 is greater than or equal to 1wt% and less than or equal to 10wt%; the solid electrolyte slurry 3 is coated on the outer surface of the polar active layer 2 in an environment with a dew point of -50°C on the surface 22 to form a slurry-coated pole piece 7 including the polar active layer 2 and the solid electrolyte slurry 3, wherein the solid electrolyte slurry 3 coated on the outer surface 22 of the polar active layer 2 A thickness greater
  • a temperature of the aforementioned negative pressure heating process is greater than or equal to 100° C. and less than or equal to 150° C.
  • a time of the aforementioned negative pressure heating process is greater than or equal to 10 minutes.
  • the binder is polyvinylidene fluoride (PVDF). The time of the aforementioned negative pressure heating process can be adjusted until the solid electrolyte slurry 3 is completely dried to form the solid electrolyte layer 6 .
  • the positive electrode plate 60 produced by the method for preparing a pole piece using a solid electrolyte material of the present invention has a solid electrolyte layer 1 formed on the outer surface 22 of the positive electrode active layer 20, and the solid electrolyte layer 1 is tightly The outer surface 22 of the positive electrode active layer 20 is adhered and covered, thereby reducing the solid-state interface impedance between the solid electrolyte layer 1 and the positive electrode active layer 20 to increase the solid-state ionic conductivity.
  • the negative electrode pole piece 61 produced by a method for preparing a pole piece using a solid electrolyte material of the present invention has the solid electrolyte layer 1 formed on the outer surface 22 of the negative electrode active layer 21, and the solid electrolyte layer 1 is tightly adhered to and covers the outer surface 22 of the negative electrode active layer 21, thereby reducing the solid-state interface impedance between the solid electrolyte layer 1 and the negative electrode active layer 21 to increase the solid-state ionic conductivity.
  • the thickness of the solid electrolyte slurry 3 coated on the outer surface 22 of the polar active layer 2 can be adjusted as required, so as to be suitable for manufacturing A winding process or a lamination process of the battery cell.
  • the negative electrode carrier plate 5 can be made of copper foil.
  • the positive electrode carrier 4 can be made of aluminum foil.
  • the material constituting the positive electrode active layer 20 can also be LiMnO 2 , LiMn 2 O 4 , Li 2 Cr 2 O 7 , Li 2 CrO 4 , LiNiO 2 , LiFeO 2 , LiNi x Co (1-x) O 2 , LiMn 0.5 Ni 0.5 O 2 , LiMn 1/3 Co 1/3 Ni 1/3 O 2 , or a combination thereof.
  • the material constituting the negative electrode active layer 21 can also be lithium mixed metal oxide or can also be produced by ball milling of commercial silicon powder, and a carbon film is coated on the surface of the silicon material.
  • FIG. 3 is a schematic cross-sectional view of a step of a method for preparing a solid electrolyte sheet using a solid electrolyte material according to the present invention.
  • a preparation method of a solid electrolyte sheet using a solid electrolyte material of the present invention includes the following steps: coating the aforementioned solid electrolyte slurry 3 on a release paper 80 in an environment with a dew point of -50° C., wherein the coating A thickness of the solid electrolyte slurry 3 on the release paper 80 is greater than or equal to 10 ⁇ m and less than or equal to 100 ⁇ m; a negative pressure heating process is performed to dry the solid electrolyte slurry 3 to form a solid electrolyte sheet 8 on the release paper.
  • the release paper 80 facilitates the separation of the solid electrolyte sheet 8 therefrom.
  • the aforementioned negative pressure heating process is performed in a negative pressure environment greater than or equal to -2000Pa and less than or equal to -500Pa, and a temperature of the aforementioned negative pressure heating process is greater than or equal to 100°C and less than or equal to 150°C, the aforementioned negative pressure heating A time of the autoclaving process is greater than or equal to 10 minutes. The time of the aforementioned negative pressure heating process can be adjusted until the solid electrolyte slurry 3 is completely dried to form the solid electrolyte sheet 8 .
  • the thickness of the solid electrolyte slurry 3 coated on the release paper 80 (corresponding to a thickness of the solid electrolyte sheet 8 formed after complete drying) can be adjusted as required.
  • the aforementioned solid electrolyte slurry 3 is coated on a porous material in an environment with a dew point of -50°C; and then the aforementioned negative pressure heating process is performed to dry the solid electrolyte slurry 3 to form a solid electrolyte Sheet 8.
  • the porous material may be a fibrous cloth or a paper with a plurality of pores penetrating the upper and lower surfaces.
  • the solid electrolyte sheet 8 made of the porous material and the solid electrolyte slurry 3 has better isolation effect.
  • FIG. 4 is a schematic cross-sectional view of a specific embodiment of a battery cell using a solid electrolyte material according to the present invention.
  • a battery cell 10 using a solid electrolyte material of the present invention includes a negative pole piece 61 and a positive pole piece 60 .
  • the positive pole piece 60 and the negative pole piece 61 are prepared by the aforementioned method for preparing a pole piece using a solid electrolyte material;
  • the positive pole piece 60 includes a positive electrode carrier plate 4, a positive electrode active layer 20 and a solid electrolyte layer 1;
  • the negative electrode pole piece 61 includes a negative electrode carrier plate 5 , a negative electrode active layer 21 and a solid electrolyte layer 1 .
  • the present invention provides a preparation method (a winding process) of a battery core 10 using a solid electrolyte material, which includes the following steps: stacking the negative pole piece 61 and the positive pole piece 60 to form the battery core 10, wherein the negative pole piece The solid electrolyte layer 1 of 61 is adjacent to the solid electrolyte layer 1 of the positive pole piece 60; a slitting procedure is performed on the battery core 10; a winding procedure is performed on the slitted battery core 10; Hot-pressing process, wherein a pressure of the hot-pressing process is greater than or equal to 50MPa and less than or equal to 250MPa, a temperature of the hot-pressing process is greater than or equal to 100°C and less than or equal to 200°C, and a time of the hot-pressing process is greater than or equal to 1 minute (in a preferred embodiment, the pressure of the hot-pressing process is equal to 250MPa, the temperature of the hot-pressing process is equal to 120° C., and the time of
  • the present invention provides a method for preparing a battery core 10 using a solid electrolyte material (a lamination process), which includes the following steps: stacking the negative pole piece 61 and the positive pole piece 60 to form the battery core 10 , wherein the solid electrolyte layer 1 of the negative pole piece 61 is adjacent to the solid electrolyte layer 1 of the positive pole piece 60; a cutting procedure is performed on the battery core 10; a lamination procedure is performed on the battery core 10 after the cutting piece; and The battery core 10 is subjected to a hot pressing process, wherein the pressure of the hot pressing process is greater than or equal to 50MPa and less than or equal to 250MPa, the temperature of the hot pressing process is greater than or equal to 100°C and less than or equal to 200°C, and the time of the hot pressing process is greater than or equal to 200°C.
  • a lamination process includes the following steps: stacking the negative pole piece 61 and the positive pole piece 60 to form the battery core 10 , wherein the solid electrolyte layer 1
  • the pressure of the hot-pressing process is equal to 250MPa, the temperature of the hot-pressing process is equal to 120°C, and the time of the hot-pressing process is equal to 1 minute); and for the battery cells after the hot-pressing process 10.
  • the battery core 10 formed by stacking the negative pole piece 61 and the positive pole piece 60 needs to be After the hot pressing process, the interface between the solid electrolyte layer 1 of the negative pole piece 61 and the solid electrolyte layer 1 of the positive pole piece 60 is tightly compacted and bonded by high pressure and high temperature, thereby reducing the solid electrolyte layer 1 of the negative pole piece 61 and the solid electrolyte layer 1.
  • the solid-state interface impedance between the solid-state electrolyte layers 1 of the positive pole piece 60 increases the solid-state ionic conductivity.
  • FIG. 5 is a schematic cross-sectional view of another specific embodiment of a battery cell using a solid electrolyte material according to the present invention.
  • the main structure of a battery cell 10' of the embodiment of FIG. 5 is substantially the same as that of the battery cell 10 of the embodiment of FIG. 4 , except that it further includes a solid electrolyte sheet 8 .
  • the solid electrolyte sheet 8 is located between the solid electrolyte layer 1 of the negative pole piece 61 and the solid electrolyte layer 1 of the positive pole piece 60 , and the solid electrolyte sheet 8 is connected to the solid electrolyte layer 1 of the negative pole piece 61 and the positive pole piece respectively.
  • the solid electrolyte layers 1 of 60 are adjacent to each other.
  • the solid electrolyte sheet 8 can increase the isolation effect. By adjusting the thickness of the solid electrolyte sheet 8, the desired isolation effect can be adjusted. Therefore, a method for preparing a battery core 10 using a solid electrolyte material of the present invention, whether it is a winding process or a lamination process, is formed by stacking the negative pole piece 61 , the solid electrolyte sheet 8 and the positive pole piece 60 .
  • the battery cells 10 all need to undergo a hot pressing process, so that the interface between the solid electrolyte layer 1 of the negative pole piece 61 and the solid electrolyte sheet 8 and the interface between the solid electrolyte sheet 8 and the solid electrolyte layer 1 of the positive pole piece 60 are subjected to high pressure.
  • the high temperature is tightly compacted and bonded, thereby reducing the solid-state interface impedance between the solid electrolyte layer 1 of the negative pole piece 61 and the solid electrolyte sheet 8, and reducing the solid electrolyte sheet 8 and the solid electrolyte layer 1 of the positive pole piece 60.
  • Interface impedance to increase solid state ionic conductivity is tightly compacted and bonded, thereby reducing the solid-state interface impedance between the solid electrolyte layer 1 of the negative pole piece 61 and the solid electrolyte sheet 8, and reducing the solid electrolyte sheet 8 and the solid electrolyte layer 1 of the positive pole piece 60.
  • the present invention can clearly achieve the intended purpose of the invention, and provides a solid electrolyte material, a preparation method thereof, and a pole piece and a battery core using the solid electrolyte material, which are highly industrialized. The price of use.

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Abstract

一种固态电解质材料的制备方法，包括以下步骤：将[(Li 2S) x(P 2S 5) (100-x)] y[z] (100-y)混合成一前驱混合物，其中70≤x≤80，70≤y≤95，z为LiCl、LiBr以及LiI的其中至少一个；在一惰性气体的环境下对前驱混合物进行一机械合金工艺，以形成一机械合金后前驱物；以及在惰性气体的环境下对机械合金后前驱物进行一热处理，以形成非晶态或微晶态的一固态电解质材料，其中热处理的一温度大于或等于200℃，且小于或等于500℃，热处理的一时间大于或等于两小时，且小于或等于七小时。

Description

固态电解质材料、其制备方法及使用该固态电解质材料的极片、电池芯 技术领域
本发明有关一种固态电解质材料，尤指一种非晶或微晶固态电解质离子导体材料，其制备方法及使用该固态电解质材料的极片、电池芯。
背景技术
商用锂离子电池大部分为液态或胶态电解液，当电池容量和能量密度一直提升时，液态和胶态电解液已无法提供足够的安全保证，燃烧、爆炸等事故时常发生。有机高分子或树脂类固态电解质虽容易进行界面贴合，但其存在着电解质离子传导率过低，且热稳定性不足等问题。而无机矿物类如氧化物和硫化物的固态电解质虽可提供较好的热稳定性，但是因其存在着固态界面阻抗大，且固态离子传导率低等问题，再加上易碎等缺点，往往要加许多的添加物改良，成本高制作不易。因此，固态锂离子电池商业化应用必需解决以上问题。
有鉴于此，发明人开发出简便组装的设计，能够避免上述的缺点，安装方便，又具有成本低廉的优点，以兼顾使用弹性与经济性等考量，因此遂有本发明的产生。
发明内容
本发明所欲解决的技术问题在于如何备制一种热稳定性高的固态电解质材料、如何使用前述热稳定性高的固态电解质材料分别备制正极极片、负极极片以及如何使用前述正极极片、负极极片备制电池芯，使正极极片、负极极片及固态电解质材料之间高度黏合，以降低电池芯的固态介面阻抗，并借此增加固态离子传导率。
为解决前述问题，以达到所预期的功效，本发明提供一种固态电解质材 料，其组成为[(Li 2S) x(P 2S 5) (100-x)] y[z] (100-y)，其中70≤x≤80，70≤y≤95，z为LiCl、LiBr以及LiI的其中至少一个，其中固态电解质材料为非晶态或微晶态。
此外，本发明还提供一种固态电解质材料的制备方法，包括以下步骤：将[(Li 2S) x(P 2S 5) (100-x)] y[z] (100-y)混合成一前驱混合物，其中70≤x≤80，70≤y≤95，z为LiCl、LiBr以及LiI的其中至少一个；在一惰性气体的环境下对前驱混合物进行一机械合金工艺，以形成一机械合金后前驱物；以及在惰性气体的环境下对机械合金后前驱物进行一热处理，以形成非晶态或微晶态的一固态电解质材料，其中热处理的一温度大于或等于200℃，且小于或等于500℃，热处理的一时间大于或等于两小时，且小于或等于七小时。
此外，本发明还提供一种使用固态电解质材料的极片，包括：一载板、一极性活性层以及一固态电解质层。其中极性活性层形成于该载板之上；固态电解质层形成于极性活性层的一外表面之上；构成固态电解质层的材料包括前述固态电解质材料。
于实施例时，极性活性层为一正极活性层，极片为一正极极片。
于实施例时，极性活性层为一负极活性层，极片为一负极极片。
此外，本发明还提供一种使用固态电解质材料的极片的制备方法，包括以下步骤：将前述固态电解质材料研磨成粉末状；将粉末状的固态电解质材料与一黏结剂均匀混合搅拌以形成一固态电解质浆料；在一露点-50℃的环境中将固态电解质浆料涂布于一极性活性层的一外表面之上，以形成一浆料涂布极片；以及在大于或等于-2000Pa，且小于或等于-500Pa的一负压环境下对浆料涂布极片进行一负压加热工艺，使固态电解质浆料干燥以形成包括一固态电解质层以及极性活性层的一极片，其中负压加热工艺的一温度大于或等于100℃，且小于或等于150℃，负压加热工艺的一时间大于或等于10 分钟。借此降低固态电解质层与极性活性层之间的固态界面阻抗，以增加固态离子传导率。
于实施例时，涂布于极性活性层的外表面之上的固态电解质浆料的一厚度大于或等于10μm，且小于或等于100μm。
此外，本发明还提供一种使用固态电解质材料的电池芯，包括：前述负极极片以及前述正极极片。其中正极极片的固态电解质层与负极极片的固态电解质层结合。
此外，本发明还提供一种使用固态电解质材料的电池芯的制备方法，包括以下步骤：将前述负极极片以及前述正极极片堆迭成一电池芯，其中正极极片的固态电解质层与负极极片的固态电解质层邻接；以及对电池芯进行一热压工艺，其中热压工艺的一压力大于或等于50MPa，且小于或等于250MPa，热压工艺的一温度大于或等于100℃，且小于或等于200℃，热压工艺的一时间大于或等于1分钟。借此降低正极极片的固态电解质层与负极极片的固态电解质层之间的固态界面阻抗，以增加固态离子传导率。
于实施例时，其还包括一固态电解质薄片，位于介于正极极片的固态电解质层与负极极片的固态电解质层之间，且固态电解质薄片分别与正极极片的固态电解质层及负极极片的固态电解质层结合，其中构成固态电解质薄片的材料包括前述固态电解质材料。借此降低正极极片的固态电解质层与固态电解质薄片之间的固态界面阻抗，并降低固态电解质薄片与负极极片的固态电解质层之间的固态界面阻抗，以增加固态离子传导率。
附图说明
图1为本发明一种使用固态电解质材料的极片的一具体实施例的剖面示意图；
图2为本发明一种使用固态电解质材料的极片的制备方法的一步骤的剖面示意图；
图3为本发明一种使用固态电解质材料的固态电解质薄片的制备方法的一步骤的剖面示意图；
图4为本发明一种使用固态电解质材料的电池芯的一具体实施例的剖面示意图；
图5为本发明一种使用固态电解质材料的电池芯的另一具体实施例的剖面示意图。
附图标记说明
1固态电解质层      2极性活性层
3固态电解质浆料    4正极载板
5负极载板          6极片
7浆料涂布极片      8固态电解质薄片
9载板              10，10’电池芯
20正极活性层       21负极活性层
22外表面           60正极极片
61负极极片         80离型纸。
具体实施方式
为进一步了解本发明，以下举较佳的实施例，配合附图、附图标记，将本发明的具体构成内容及其所达成的功效详细说明如下。
本发明提供一种固态电解质材料，其组成为：[(Li 2S) x(P 2S 5) (100-x)] y[z] (100-y)，其中70≤x≤80，70≤y≤95，z为LiCl(氯化锂)、LiBr(溴化锂)以及LiI(碘化锂)的其中至少一个。此外，本发明提供一种固态电解质材料的制备方法，包括以下步骤：将[(Li 2S) x(P 2S 5) (100-x)] y[z] (100-y)混合成一前驱混合物，其中70≤x≤80，70≤y≤95，z为LiCl、LiBr以及LiI的其中至少一个；在一惰性气体的环境 下对上述前驱混合物进行一机械合金工艺，以形成一机械合金后前驱物，其中前述机械合金工艺可使前驱混合物形成较稳定状态的机械合金后前驱物；以及在惰性气体的环境下对上述机械合金后前驱物进行一热处理，以形成一固态电解质材料，其中固态电解质材料为非晶态或微晶态的固态电解质离子导体。其中前述惰性气体可为氦气、氖气、氩气、氪气、氙气，或上述气体的组合。其中前述热处理的一温度大于或等于200℃，且小于或等于500℃。前述热处理的一时间大于或等于两小时，且小于或等于七小时。前述机械合金工艺可使用一高能球磨机或一高能研磨机来进行机械合金。在一较佳实施例中，前述热处理的温度为230℃，前述热处理的时间为六小时。在一较佳实施例中，前述惰性气体为氩气。
请参阅图1，其为本发明一种使用固态电解质材料的极片的一具体实施例的剖面示意图。本发明提供一种使用固态电解质材料的一极片6，包括一载板9、一极性活性层2以及一固态电解质层1。其中极性活性层2形成于载板9之上。固态电解质层1形成于极性活性层2的一外表面22之上。其中极性活性层2可为一正极活性层20或一负极活性层21；而载板9可为一正极载板4或一负极载板5。当极性活性层2为正极活性层20时，载板9为正极载板4，极片6为一正极极片60，其中构成正极活性层20的材料包括LiCoO 2(钴酸锂)、LiFePO 4(磷酸铁锂)、镍钴锰酸锂(NCM)以及镍钴铝酸锂(NCA)的其中至少一个。当极性活性层2为负极活性层21时，载板9为负极载板5，极片6为一负极极片61，其中构成负极活性层21的材料包括石墨、硬碳、软碳、Li 4Ti 5O 12、TiNb 2O 7以及SiC(碳化硅)的其中至少一个。此外，本发明提供一种使用固态电解质材料的极片的制备方法，包括以下步骤(请同时参阅图2，其为本发明一种使用固态电解质材料的极片的制备方法的一步骤的剖面示意图)：将极性活性层2形成于载板9之上；将前述固态电解质材料研磨成粉末状；将粉末状的固态电解质材料与一黏结 剂均匀混合搅拌以形成一固态电解质浆料3，其中，黏结剂占固态电解质浆料3的比例为大于或等于1wt％，且小于或等于10wt％；在一露点-50℃的环境中将固态电解质浆料3涂布于极性活性层2的外表面22之上，以形成包括极性活性层2以及固态电解质浆料3的一浆料涂布极片7，其中涂布于极性活性层2的外表面22之上的固态电解质浆料3的一厚度大于或等于10μm，且小于或等于100μm；以及在大于或等于-2000Pa，且小于或等于-500Pa的一负压环境下对浆料涂布极片7进行一负压加热工艺，使固态电解质浆料3干燥以形成包括固态电解质层6以及极性活性层2的极片6(如图1所示)。其中前述负压加热工艺的一温度大于或等于100℃，且小于或等于150℃，前述负压加热工艺的一时间大于或等于10分钟。在一较佳实施例中，黏结剂为聚偏二氟乙烯(PVDF)。前述负压加热工艺的时间可做调整，直至固态电解质浆料3完全干燥而形成固态电解质层6为止。利用本发明的一种使用固态电解质材料的极片的制备方法所制造出来的正极极片60，其具有形成于正极活性层20的外表面22之上的固态电解质层1，固态电解质层1紧密地黏合着且包覆着正极活性层20的外表面22，借此降低固态电解质层1与正极活性层20之间的固态界面阻抗，以增加固态离子传导率。同样地，本发明的一种使用固态电解质材料的极片的制备方法所制造出来的负极极片61，其具有形成于负极活性层21的外表面22之上的固态电解质层1，固态电解质层1紧密地黏合着且包覆着负极活性层21的外表面22，借此降低固态电解质层1与负极活性层21之间的固态界面阻抗，以增加固态离子传导率。其中涂布于极性活性层2的外表面22之上的固态电解质浆料3的厚度(相关于完全干燥后所形成的固态电解质层6的一厚度)可随需求来调整，以适用于制作的电池芯的一卷绕工艺或一迭片工艺。在一较佳的实施例中，负极载板5可由铜箔所构成。在一较佳的实施例中，正极载板4可由铝箔所构成。
在一些实施例中，构成正极活性层20的材料亦可为LiMnO 2、LiMn 2O 4、 Li 2Cr 2O 7、Li 2CrO 4、LiNiO 2、LiFeO 2、LiNi xCo (1-x)O 2、LiMn 0.5Ni 0.5O 2、LiMn 1/3Co 1/3Ni 1/3O 2、或上述的组合。在一些实施例中，构成负极活性层21的材料亦可为锂金属混合氧化物(lithium mixed metal oxide)或亦可分别由商用硅粉末球磨后而成，且在硅材料表面包覆碳膜。
请参阅图3，其为本发明一种使用固态电解质材料的固态电解质薄片的制备方法的一步骤的剖面示意图。本发明一种使用固态电解质材料的固态电解质薄片的制备方法，包括以下步骤：在一露点-50℃的环境中将前述固态电解质浆料3涂布于一离型纸80之上，其中涂布于离型纸80之上的固态电解质浆料3的一厚度大于或等于10μm，且小于或等于100μm；进行一负压加热工艺，使固态电解质浆料3干燥以形成一固态电解质薄片8于离型纸80之上；以及将固态电解质薄片8与离型纸80分离，其中离型纸80有利于使固态电解质薄片8与其分离。其中前述负压加热工艺在大于或等于-2000Pa，且小于或等于-500Pa的一负压环境下进行，前述负压加热工艺的一温度大于或等于100℃，且小于或等于150℃，前述负压加热工艺的一时间大于或等于10分钟。前述负压加热工艺的时间可做调整，直至固态电解质浆料3完全干燥而形成固态电解质薄片8为止。涂布于离型纸80之上的固态电解质浆料3的厚度(相关于完全干燥后所形成的固态电解质薄片8的一厚度)可随需求来调整。在一些实施例中，在一露点-50℃的环境中将前述固态电解质浆料3涂布于一多孔材料上；再进行前述负压加热工艺，使固态电解质浆料3干燥以形成固态电解质薄片8。其中多孔材料可为具有多个穿透上下表面的孔隙的一纤维布或一纸。由多孔材料与固态电解质浆料3所制造而成的固态电解质薄片8，其隔离效果更佳。
请参阅图4，其为本发明一种使用固态电解质材料的电池芯的一具体实施例的剖面示意图。本发明的使用固态电解质材料的一电池芯10包括一负极极片61以及一正极极片60。其中正极极片60以及负极极片61由前述的 本发明的使用固态电解质材料的极片的制备方法所制备；正极极片60包括一正极载板4、一正极活性层20以及一固态电解质层1；负极极片61包括一负极载板5、一负极活性层21以及一固态电解质层1。此外，本发明提供一种使用固态电解质材料的电池芯10的制备方法(一卷绕工艺)，包括以下步骤：将负极极片61以及正极极片60堆迭成电池芯10，其中负极极片61的固态电解质层1与正极极片60的固态电解质层1相邻接；对电池芯10进行一分条程序；对分条后的电池芯10进行一卷绕程序；对电池芯10进行一热压工艺，其中热压工艺的一压力大于或等于50MPa，且小于或等于250MPa，热压工艺的一温度大于或等于100℃，且小于或等于200℃，热压工艺的一时间大于或等于1分钟(在一较佳的实施例中，热压工艺的压力等于250MPa，热压工艺的温度等于120℃，热压工艺的时间等于1分钟)；以及对热压工艺后的电池芯10进行一入壳程序、一雷射封口程序以及一化成分容程序。在另一实施例中，本发明提供一种使用固态电解质材料的电池芯10的制备方法(一迭片工艺)，包括以下步骤：将负极极片61以及正极极片60堆迭成电池芯10，其中负极极片61的固态电解质层1与正极极片60的固态电解质层1相邻接；对电池芯10进行一裁片程序；对裁片后的电池芯10进行一迭片程序；以及对电池芯10进行热压工艺，其中热压工艺的压力大于或等于50MPa，且小于或等于250MPa，热压工艺的温度大于或等于100℃，且小于或等于200℃，热压工艺的时间大于或等于1分钟(在一较佳的实施例中，热压工艺的压力等于250MPa，热压工艺的温度等于120℃，热压工艺的时间等于1分钟)；以及对热压工艺后的电池芯10进行一入壳程序、一雷射封口程序以及一化成分容程序。因此，本发明的一种使用固态电解质材料的电池芯10的制备方法，不论是卷绕工艺或是迭片工艺，负极极片61以及正极极片60所堆迭而成的电池芯10皆需经过热压工艺，使得负极极片61的固态电解质层1与正极极片60的固态电解质层1之间的介面经过高压高温紧密 压实黏合，借此降低负极极片61的固态电解质层1与正极极片60的固态电解质层1之间的固态界面阻抗，以增加固态离子传导率。
请参阅图5，其为本发明一种使用固态电解质材料的电池芯的另一具体实施例的剖面示意图。图5的实施例的一电池芯10’的主要结构与图4的实施例的电池芯10的结构大致相同，惟，其还包括一固态电解质薄片8。其中固态电解质薄片8位于介于负极极片61的固态电解质层1与正极极片60的固态电解质层1之间，且固态电解质薄片8分别与负极极片61的固态电解质层1与正极极片60的固态电解质层1相邻接。固态电解质薄片8可增加隔离效果。通过调整固态电解质薄片8的厚度，可调整所需的隔离效果。因此，本发明的一种使用固态电解质材料的电池芯10的制备方法，不论是卷绕工艺或是迭片工艺，负极极片61、固态电解质薄片8以及正极极片60所堆迭而成的电池芯10皆需经过热压工艺，使得负极极片61的固态电解质层1与固态电解质薄片8之间的介面以及固态电解质薄片8与正极极片60的固态电解质层1之间的介面经过高压高温紧密压实黏合，借此降低负极极片61的固态电解质层1与固态电解质薄片8之间的固态界面阻抗，以及降低固态电解质薄片8与正极极片60的固态电解质层1之间的固态界面阻抗，以增加固态离子传导率。
以上所述乃是本发明的具体实施例及所运用的技术手段，根据本文的公开或教导可衍生推导出许多的变更与修正，仍可视为本发明的构想所作的等效改变，其所产生的作用仍未超出说明书及附图所涵盖的实质精神，均应视为在本发明的技术范畴之内，合先陈明。
综上所述，依上文所公开的内容，本发明确可达到发明的预期目的，提供一种固态电解质材料、其制备方法及使用该固态电解质材料的极片、电池芯，极具产业上利用的价植。

Claims (10)

  1. 一种固态电解质材料，其特征在于，
    其组成为[(Li 2S) x(P 2S 5) (100-x)] y[z] (100-y)，其中70≤x≤80，70≤y≤95，z为LiCl、LiBr以及LiI的其中至少一个。
  2. 如权利要求1所述的固态电解质材料，其特征在于，该固态电解质材料为非晶态或微晶态。
  3. 一种如权利要求1所述的固态电解质材料的制备方法，其特征在于，包括以下步骤：
    将[(Li 2S) x(P 2S 5) (100-x)] y[z] (100-y)混合成一前驱混合物，其中70≤x≤80，70≤y≤95，z为LiCl、LiBr以及LiI的其中至少一个；
    在一惰性气体的环境下对该前驱混合物进行一机械合金工艺，以形成一机械合金后前驱物；以及
    在该惰性气体的环境下对该机械合金后前驱物进行一热处理，以形成该固态电解质材料，其中该热处理的一温度大于或等于200℃，且小于或等于500℃，该热处理的一时间大于或等于两小时，且小于或等于七小时。
  4. 一种使用如权利要求1所述的固态电解质材料的极片，其特征在于，包括：
    一载板；
    一极性活性层，形成于该载板之上；以及
    一固态电解质层，形成于该极性活性层的一外表面之上，其中构成该固态电解质层的材料包括该固态电解质材料。
  5. 如权利要求4所述的极片，其特征在于，该极性活性层为一正极活性层，该极片为一正极极片。
  6. 如权利要求4所述的极片，其特征在于，该极性活性层为一负极活性层，该极片为一负极极片。
  7. 一种如权利要求4所述的极片的制备方法，其特征在于，包括以下步骤：
    将该极性活性层形成于该载板之上；
    将[(Li 2S) x(P 2S 5) (100-x)] y[z] (100-y)混合成一前驱混合物，其中70≤x≤80，70≤y≤95，z为LiCl、LiBr以及LiI的其中至少一个；
    在一惰性气体的环境下对该前驱混合物进行一机械合金工艺，以形成一机械合金后前驱物；
    在该惰性气体的环境下对该机械合金后前驱物进行一热处理，以形成该固态电解质材料；
    将该固态电解质材料研磨成粉末状；
    将粉末状的该固态电解质材料与一黏结剂均匀混合搅拌以形成一固态电解质浆料；
    在一露点-50℃的环境中将该固态电解质浆料涂布于该极性活性层的该外表面之上，以形成一浆料涂布极片；以及
    在大于或等于-2000Pa，且小于或等于-500Pa的一负压环境下对该浆料涂布极片进行一负压加热工艺，使该固态电解质浆料干燥以形成包括该固态电解质层以及该极性活性层的该极片，其中该负压加热工艺的一温度大于或等于100℃，且小于或等于150℃，该负压加热工艺的一时间大于或等于10分钟。
  8. 一种使用如权利要求4所述的极片的电池芯，其特征在于，包括：
    两个极片，分别为一正极极片以及一负极极片，其中该正极极片的该极性活性层为一正极活性层，该负极极片的该极性活性层为一负极活性层，其中该正极极片的该固态电解质层与该负极极片的该固态电解质层结合。
  9. 如权利要求8所述的电池芯，其特征在于，还包括一固态电解质薄片，该固态电解质薄片包括该固态电解质材料，该固态电解质薄片介于该正极极 片的该固态电解质层与该负极极片的该固态电解质层之间，且该固态电解质薄片的反向两侧面分别与该正极极片的该固态电解质层及该负极极片的该固态电解质层结合。
  10. 一种如权利要求8所述的电池芯的制备方法，其特征在于，包括以下步骤：
    将该负极极片以及该正极极片堆迭成该电池芯，其中该正极极片的该固态电解质层与该负极极片的该固态电解质层邻接；以及
    对该电池芯进行一热压工艺，该热压工艺的一压力大于或等于50MPa，且小于或等于250MPa，该热压工艺的一温度大于或等于100℃，且小于或等于200℃，该热压工艺的一时间大于或等于1分钟。
PCT/CN2021/092091 2021-05-07 2021-05-07 固态电解质材料、其制备方法及使用该固态电解质材料的极片、电池芯 WO2022233023A1 (zh)

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JP2001250580A (ja) * 2000-03-06 2001-09-14 Masahiro Tatsumisuna 高リチウムイオン伝導性硫化物セラミックスおよびこれを用いた全固体電池
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