WO2023030026A1 - Method for preparing sulfide solid electrolyte material and application thereof - Google Patents

Method for preparing sulfide solid electrolyte material and application thereof Download PDF

Info

Publication number
WO2023030026A1
WO2023030026A1 PCT/CN2022/113370 CN2022113370W WO2023030026A1 WO 2023030026 A1 WO2023030026 A1 WO 2023030026A1 CN 2022113370 W CN2022113370 W CN 2022113370W WO 2023030026 A1 WO2023030026 A1 WO 2023030026A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid electrolyte
gep
positive electrode
sulfide solid
sheet
Prior art date
Application number
PCT/CN2022/113370
Other languages
French (fr)
Chinese (zh)
Inventor
朱金辉
陈振营
张希
Original Assignee
上海屹锂新能源科技有限公司
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 上海屹锂新能源科技有限公司 filed Critical 上海屹锂新能源科技有限公司
Publication of WO2023030026A1 publication Critical patent/WO2023030026A1/en

Links

Images

Classifications

    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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

Definitions

  • the invention belongs to the technical field of energy materials, and relates to a preparation method and application of a sulfide solid-state electrolyte material applied in the field of solid-state batteries, in particular to a sulfide electrolyte material Li a M b P c S d (M is Al, Ga , one or more of In, Ta, a, b, c, d>0) preparation method and its application in all-solid-state batteries.
  • Lithium-ion batteries are widely used in markets such as mobile electronic devices and electric vehicles due to their high energy density and high power density.
  • Current commercial lithium batteries have safety concerns due to the presence of flammable liquid electrolytes.
  • Electric vehicles require safer lithium-ion batteries with higher energy density to extend driving distance, provide higher power density to shorten charging time, and maintain longer cycle life to reduce maintenance costs.
  • Higher energy density is achieved by increasing the battery size or the number of packed batteries, which also means increasing the amount of flammable electrolyte in the device, which raises more serious safety concerns.
  • Replacing flammable liquid electrolytes with flame-retardant inorganic solid electrolytes is a feasible way to improve battery safety.
  • the use of solid electrolytes can also simplify battery design in the absence of hazardous and liquid organic solvents. Direct stacking of multilayer solid-state batteries in a package can provide high operating voltage and save effective battery volume, paving the way for electric vehicle applications.
  • the Chinese patent "A Solid Electrolyte Sheet and a Preparation Method for a Sulfide Solid Electrolyte Sheet” with the announcement number CN201911384502 discloses a sulfide solid electrolyte with a core-shell structure and a preparation method.
  • the structure of the solid electrolyte sheet can improve
  • the strength of the solid electrolyte helps to improve the success rate of the preparation of the electrolyte sheet.
  • the preparation of the sulfide solid electrolyte sheet by the polymer fiber skeleton has great strength and structural stability, which is conducive to reducing the thickness of the solid electrolyte sheet. It is possible to prepare sulfide all-solid-state batteries with high energy density.
  • the object of the present invention is to provide a sulfide solid electrolyte material Li a M b P c S d (M is one or more of Al, Ga, In, Ta, a, b, c, d>0) preparation method and its application in all-solid-state batteries.
  • the all-solid-state battery based on this solid-state electrolyte has the characteristics of low cost, high safety, high charge-discharge specific capacity, and excellent cycle stability.
  • the present invention relates to a Li 10 GeP 2 S 12 type sulfide solid electrolyte, whose general chemical formula is Li a M b P c S d , wherein, M is one or more of Al, Ga, In, Ta, a,b,c,d>0.
  • the invention forms a novel solid electrolyte by replacing the Ge element in the traditional Li 10 GeP 2 S 12 type sulfide solid electrolyte.
  • the raw material of the solid electrolyte comprises the following components:
  • Li source one or more combinations of LiH, Li 2 S 2 , Li 2 S;
  • S source one or more combinations of S, H 2 S, P 2 S 5 , P 4 S 9 , P 4 S 3 , Li 2 S 2 , Li 2 S, M 2 S 3 ;
  • P source one or more combinations of P, P 2 S 5 , P 4 S 9 , P 4 S 3 , P 4 S 6 , P 4 S 5 ;
  • the M source is: one or more combinations of In 2 S 2 , In 2 S 3 , Al 2 S 3 , Ga 2 S 3 , and Ta 2 S 3 .
  • the mass ratio of Li to M in the solid electrolyte is 2-10:1.
  • the present invention also relates to a preparation method of Li 10 GeP 2 S 12 type sulfide solid electrolyte, comprising the following steps:
  • step S2 Compressing the initial solid electrolyte powder obtained in step S1 under 300-900 MPa to obtain an initial solid electrolyte sheet;
  • step S3 Seal the initial solid electrolyte sheet obtained in step S2 in a quartz tube or glass tube, and vacuum seal the tube ( ⁇ 10-4 Pa), calcining at a temperature of 500-650°C for 12-60 hours to obtain a sulfide solid electrolyte material .
  • Li 2 S , P 2 S 5 , and M 2 S 3 in an appropriate molar ratio are mixed and ball-milled in step S1 to obtain an initial solid electrolyte powder.
  • the ball mill is a high-energy mechanical ball mill
  • the rotational speed of the ball mill is 500-650 rpm
  • the milling time is 12-60 hours.
  • the invention also relates to the application of a Li 10 GeP 2 S 12 type sulfide solid electrolyte in the preparation of an all-solid battery.
  • A1 Mix the positive electrode material, conductive carbon black and Li 10 GeP 2 S 12 type sulfide solid electrolyte material, and grind them evenly to obtain positive electrode powder; disperse the positive electrode powder in 4% polyvinylidene fluoride-N-methyl Pyrrolidone solution, magnetically stirred evenly, and then coated on aluminum foil to prepare a positive electrode sheet;
  • the thickness of the solid electrolyte sheet is 200-800 ⁇ m.
  • the present invention also relates to a sulfide-based all-solid-state battery, comprising a positive electrode part, a negative electrode part, and an electrolyte part; at least one of the positive electrode part, the negative electrode part, and the electrolyte part includes the Li 10 GeP 2 S 12 type sulfide solid electrolyte.
  • the positive electrode part is constructed by mixing the positive electrode active material and the Li 10 GeP 2 S 12 type sulfide solid electrolyte, and the positive electrode active material is a spinel-type transition metal oxide with a layered structure of lithium transition metal oxides, olivine, or a mixture of two or more of these materials.
  • the weight percentage of the Li 10 GeP 2 S 12 type sulfide solid electrolyte in the positive electrode part to the total weight of the positive electrode part is 0-40wt%.
  • the positive electrode active material is LiCoO 2 , LiFePO 4 , LiNix Co y Mn 1 -xy O 2 , LiNi x Co y Al 1-xy O 2 , LiNi 0.5 Mn 1.5 O 4 , LiFe One of x Mn 1-x PO 4 or a mixture of two or more.
  • the negative electrode part is constructed by mixing the negative electrode active material and the Li 10 GeP 2 S 12 type sulfide solid electrolyte, and the negative electrode active material is a carbon series material, a Si-containing carbon material or an olivine structure Transition metal material; the carbon series material is artificial graphite, natural graphite, hard carbon or graphene; the transition metal material with olivine structure is Li 4 Ti 5 O 12 or LiNbTi 2 O 7 .
  • the weight percentage of the Li 10 GeP 2 S 12 type sulfide solid electrolyte in the negative electrode part to the total weight of the negative electrode part is 0-40wt%.
  • the present invention also relates to a method for preparing an all-solid-state battery; first, the positive electrode material is prepared, and the electrode material, conductive carbon black and sulfide solid electrolyte material are mixed according to a certain ratio (such as, 2-3:1:5-6); Grinding and mixing uniformly to obtain positive electrode powder; dispersing the positive electrode powder in 4% polyvinylidene fluoride-N-methylpyrrolidone solution, stirring evenly by magnetic force, and coating on aluminum foil to obtain positive electrode sheet.
  • the reason for the positive composite sulfide electrolyte is to improve the ionic conductivity.
  • the sulfide solid electrolyte material powder is placed in a tablet mold and pressed into a solid electrolyte sheet, then the positive electrode sheet is placed on one side of the solid electrolyte, and pressed with pressure, and finally the lithium battery is attached to the other side of the solid electrolyte. Foil, pressed into an all-solid-state battery in a sandwich structure.
  • Fig. 1 is the XRD pattern of the Li 10 InP 2 S 12 sulfide solid state electrolyte prepared according to Example 1;
  • Fig. 2 is the cycle performance of the all-solid-state battery prepared according to Example 1;
  • Fig. 3 is the first charge and discharge curve of the all-solid-state battery prepared according to Example 1;
  • Fig. 4 is the conductivity curve of the electrolyte prepared according to Examples 1-4 and Comparative Examples 1-3; Wherein, (A) is the impedance spectrum of the stainless steel symmetric cell assembled with the prepared electrolyte; (B) is calculated The lithium ion conductivity of the prepared electrolyte;
  • Fig. 5 is a charge-discharge curve of the 50th cycle of the all-solid-state battery prepared according to Examples 1-4 and Comparative Examples 1-3.
  • This example relates to the preparation of Li 10 InP 2 S 12 sulfide solid electrolyte and its all-solid-state battery; including the following steps:
  • step (2) Place 40 mg of the powder obtained in step (1) in a tableting mold with a diameter of 12 mm, and press at 600 MPa to form a solid electrolyte tablet.
  • step (3) Put the sheet-shaped electrolyte obtained in step (2) into a quartz tube under an argon atmosphere, and vacuum seal the tube ( ⁇ 10 ⁇ 4 Pa).
  • step (3) heat-treating the solid electrolyte sheet obtained in step (3) at 550° C. for 12 hours to obtain a sulfide solid electrolyte material.
  • This comparative example relates to Li 10 SiP 2 S 12 sulfide solid electrolyte and its preparation; including the following steps:
  • Li 2 S, P 2 S 5 and dopant SiS 2 were mixed and subjected to high-energy planetary ball milling.
  • the rotational speed and time of high-energy planetary ball milling were 550rpm and 48h, so as to obtain the initial solid electrolyte material.
  • step (2) Place 40 mg of the solid electrolyte raw material obtained in step (1) in a tableting mold with a diameter of 12 mm, and press at 600 MPa to form a solid electrolyte tablet.
  • step (3) Put the sheet electrolyte obtained in step (2) into a quartz tube under an argon atmosphere, and vacuum seal the tube ( ⁇ 10 -4 Pa);
  • step (3) heat-treating the solid electrolyte sheet obtained in step (3) at 550° C. for 24 hours to obtain a sulfide solid electrolyte material.
  • the all-solid-state batteries made in the above-mentioned Examples 1-4 and Comparative Examples 1-3 were installed in a special battery testing device in a glove box to test the battery performance, and at the same time, the assembled battery was subjected to a 0.5C constant current battery charge and discharge test , the charge and discharge range is 2–4.2V, and the test temperature is at room temperature in a 25°C environment.
  • the sulfide solid electrolyte prepared in Example 1 was subjected to XRD test, and the test results are shown in Fig. 1 .
  • the all-solid-state battery made in Example 1 is a 2032-type button battery.
  • the battery is subjected to a constant current charge and discharge test at 0.5C.
  • the charge and discharge voltage range is 2–4.2V, and the test temperature is 25°C.
  • the charge and discharge cycle is shown in Figure 3
  • the first charge and discharge curve is shown in Figure 2.
  • the conductivity of each electrolyte is shown in Table 1.
  • the 50th cycle charge and discharge curve (Fig.
  • Table 1 The conductivity of the electrolytes prepared according to Examples 1-4 and Comparative Examples 1-3.
  • the present invention has the following beneficial effects:
  • the prepared sulfide solid electrolyte material has good chemical stability

Abstract

Disclosed in the present invention are a method for preparing sulfide solid electrolyte material and an application thereof. The electrolyte has a structure of Li10GeP2S12, with a general chemical formula of LiaMbPcSd (M being one or more of Al, Ga, In, or Ta, and a, b, c, d >0). A Li10GeP2S12-type solid state electrolyte has the highest lithium ion conductivity, but the high cost of currently developed solid state electrolytes of this type prevents further practical application thereof.

Description

一种硫化物固态电解质材料制备方法和应用A kind of preparation method and application of sulfide solid electrolyte material 技术领域technical field
本发明属于能源材料技术领域，涉及一种应用于固态电池领域中的硫化物固态电解质材料制备方法和应用，尤其涉及一种硫化物电解质材料Li aM bP cS d(M为Al、Ga、In、Ta中的一种或多种，a,b,c,d>0)制备方法及其在全固态电池中的应用。 The invention belongs to the technical field of energy materials, and relates to a preparation method and application of a sulfide solid-state electrolyte material applied in the field of solid-state batteries, in particular to a sulfide electrolyte material Li a M b P c S d (M is Al, Ga , one or more of In, Ta, a, b, c, d>0) preparation method and its application in all-solid-state batteries.
背景技术Background technique
锂离子电池由于具有高能量密度和高功率密度的特点，在移动电子设备和电动汽车等市场得到了广泛的应用。由于存在易燃液体电解质，目前商用锂电池存在安全问题。电动汽车需要更安全、能量密度更高的锂电池，以延长行驶距离，提供更高的功率密度以缩短充电时间，保持更长的循环寿命以降低维护成本。更高的能量密度是通过增加电池尺寸或包装电池的数量来实现的，这也意味着增加装置中易燃电解质的量，从而引发更严重的安全问题。用阻燃的无机固体电解质代替易燃的液体电解质是提高电池安全性的可行方法。在没有危险和流动性有机溶剂的情况下，使用固体电解质也可以简化电池设计。将多层固态电池直接堆叠在一个封装中，可以提供较高的工作电压，并节省有效电池体积，为电动汽车的应用铺平了道路。Lithium-ion batteries are widely used in markets such as mobile electronic devices and electric vehicles due to their high energy density and high power density. Current commercial lithium batteries have safety concerns due to the presence of flammable liquid electrolytes. Electric vehicles require safer lithium-ion batteries with higher energy density to extend driving distance, provide higher power density to shorten charging time, and maintain longer cycle life to reduce maintenance costs. Higher energy density is achieved by increasing the battery size or the number of packed batteries, which also means increasing the amount of flammable electrolyte in the device, which raises more serious safety concerns. Replacing flammable liquid electrolytes with flame-retardant inorganic solid electrolytes is a feasible way to improve battery safety. The use of solid electrolytes can also simplify battery design in the absence of hazardous and liquid organic solvents. Direct stacking of multilayer solid-state batteries in a package can provide high operating voltage and save effective battery volume, paving the way for electric vehicle applications.
然而，固态电池发展的关键问题之一是在室温下获得具有高锂离子电导率的固体电解质。近年来，人们投入了大量精力来探索无机固体电解质的新家族，包括硫化物、氮化物、氢化物、卤化物、磷酸盐和氧化物。与O 2-相比，S 2-具有更大的离子半径和更高的极化率,因而硫化物固态电解质比氧化物固态电解质具有更高的离子电导率，室温下可达10 -3S/cm。 However, one of the key issues in the development of solid-state batteries is to obtain solid electrolytes with high Li-ion conductivity at room temperature. In recent years, much effort has been devoted to exploring new families of inorganic solid electrolytes, including sulfides, nitrides, hydrides, halides, phosphates, and oxides. Compared with O 2- , S 2- has a larger ionic radius and higher polarizability, so the sulfide solid electrolyte has a higher ionic conductivity than the oxide solid electrolyte, which can reach 10 -3 S at room temperature /cm.
同时公告号为CN201911384502的中国专利“一种固态电解质片及硫化物固态电解质片的制备方法”公开了一种核壳结构的硫化物固体电解质及制备方法，其所述固态电解质片的结构能提高固态电解质的强度，有助于提高电解质片的制备成功率，采用聚合物纤维骨架制备硫化物固态电解质片本身就有很大的强度和结构稳定性，有利于降低固态电解质片的厚度，为进一步制备高能量密度的硫化物全固态电池提供可能性。但其不足之处在于包含在固态电解质中的纤维骨架会导致固态电解质片的厚度大大增加，从而极大的限制了所组装全固态电池的能量密度；并且，固态电解质中含有的Ge等元素， 会导致其成本过高，难以进一步大规模应用。At the same time, the Chinese patent "A Solid Electrolyte Sheet and a Preparation Method for a Sulfide Solid Electrolyte Sheet" with the announcement number CN201911384502 discloses a sulfide solid electrolyte with a core-shell structure and a preparation method. The structure of the solid electrolyte sheet can improve The strength of the solid electrolyte helps to improve the success rate of the preparation of the electrolyte sheet. The preparation of the sulfide solid electrolyte sheet by the polymer fiber skeleton has great strength and structural stability, which is conducive to reducing the thickness of the solid electrolyte sheet. It is possible to prepare sulfide all-solid-state batteries with high energy density. But its disadvantage is that the fiber skeleton contained in the solid electrolyte will lead to a great increase in the thickness of the solid electrolyte sheet, which greatly limits the energy density of the assembled all-solid-state battery; and the elements such as Ge contained in the solid electrolyte, It will cause its cost to be too high, and it is difficult to further apply it on a large scale.
发明内容Contents of the invention
本发明的目的在于提供一种硫化物固态电解质材料Li aM bP cS d(M为Al、Ga、In、Ta中的一种或多种，a,b,c,d>0)制备方法及其在全固态电池中的应用。基于该固态电解质的全固态电池，具有低成本，高安全性，高充放电比容量，优异的循环稳定性等特点。 The object of the present invention is to provide a sulfide solid electrolyte material Li a M b P c S d (M is one or more of Al, Ga, In, Ta, a, b, c, d>0) preparation method and its application in all-solid-state batteries. The all-solid-state battery based on this solid-state electrolyte has the characteristics of low cost, high safety, high charge-discharge specific capacity, and excellent cycle stability.
本发明的目的是通过以下技术方案来实现的：The purpose of the present invention is achieved through the following technical solutions:
本发明涉及一种Li 10GeP 2S 12型硫化物固态电解质，其化学通式为Li aM bP cS d，其中，M为Al、Ga、In、Ta中的一种或多种，a,b,c,d>0。 The present invention relates to a Li 10 GeP 2 S 12 type sulfide solid electrolyte, whose general chemical formula is Li a M b P c S d , wherein, M is one or more of Al, Ga, In, Ta, a,b,c,d>0.
本发明通过对传统的Li 10GeP 2S 12型硫化物固态电解质中的Ge元素进行替换，形成一种新型的固态电解质。 The invention forms a novel solid electrolyte by replacing the Ge element in the traditional Li 10 GeP 2 S 12 type sulfide solid electrolyte.
作为本发明的一个实施方案，所述固态电解质的原料包含以下成分：As an embodiment of the present invention, the raw material of the solid electrolyte comprises the following components:
Li源：LiH、Li 2S 2、Li 2S中的一种或多种组合物； Li source: one or more combinations of LiH, Li 2 S 2 , Li 2 S;
S源：S、H 2S、P 2S 5、P 4S 9、P 4S 3、Li 2S 2、Li 2S、M 2S 3中的一种或多种组合物； S source: one or more combinations of S, H 2 S, P 2 S 5 , P 4 S 9 , P 4 S 3 , Li 2 S 2 , Li 2 S, M 2 S 3 ;
P源：P、P 2S 5、P 4S 9、P 4S 3、P 4S 6、P 4S 5中的一种或多种组合物； P source: one or more combinations of P, P 2 S 5 , P 4 S 9 , P 4 S 3 , P 4 S 6 , P 4 S 5 ;
M源为：In 2S 2、In 2S 3、Al 2S 3、Ga 2S 3、Ta 2S 3中的一种或多种组合物。 The M source is: one or more combinations of In 2 S 2 , In 2 S 3 , Al 2 S 3 , Ga 2 S 3 , and Ta 2 S 3 .
作为本发明的一个实施方案，所述固态电解质中Li与M的质量比为2-10:1。As an embodiment of the present invention, the mass ratio of Li to M in the solid electrolyte is 2-10:1.
本发明还涉及一种Li 10GeP 2S 12型硫化物固态电解质的制备方法，包括以下步骤： The present invention also relates to a preparation method of Li 10 GeP 2 S 12 type sulfide solid electrolyte, comprising the following steps:
S1、将Li、S、P、M源混合球磨，得到初始固态电解质粉末；S1. Mix and ball-mill Li, S, P, and M sources to obtain initial solid electrolyte powder;
S2、将步骤S1得到的初始固态电解质粉末，在300–900MPa下压片，得到初始固态电解质片；S2. Compressing the initial solid electrolyte powder obtained in step S1 under 300-900 MPa to obtain an initial solid electrolyte sheet;
S3、将步骤S2得到的初始固态电解质片密封在石英管或玻璃管中，并真空封管(～10 –4Pa)，煅烧温度500–650℃，时间12–60h，得到硫化物固态电解质材料。 S3. Seal the initial solid electrolyte sheet obtained in step S2 in a quartz tube or glass tube, and vacuum seal the tube (~ 10-4 Pa), calcining at a temperature of 500-650°C for 12-60 hours to obtain a sulfide solid electrolyte material .
在一些实施例中，步骤S1中将适当摩尔比的Li 2S、P 2S 5、M 2S 3混合球磨，得到初始固态电解质粉末。 In some embodiments, Li 2 S , P 2 S 5 , and M 2 S 3 in an appropriate molar ratio are mixed and ball-milled in step S1 to obtain an initial solid electrolyte powder.
作为本发明的一个实施方案，所述球磨为高能机械球磨，所述球磨的转速为500–650rpm，球磨时间为12–60h。As an embodiment of the present invention, the ball mill is a high-energy mechanical ball mill, the rotational speed of the ball mill is 500-650 rpm, and the milling time is 12-60 hours.
本发明还涉及一种Li 10GeP 2S 12型硫化物固态电解质在制备全固态电池中的应用。 The invention also relates to the application of a Li 10 GeP 2 S 12 type sulfide solid electrolyte in the preparation of an all-solid battery.
作为本发明的一个实施方案，具体包括：As an embodiment of the present invention, specifically include:
A1、将正极材料、导电炭黑以及Li 10GeP 2S 12型硫化物固态电解质材料混合，将其 研磨均匀后得到正极粉末；将正极粉末分散于4％的聚偏氟乙烯-N-甲基吡咯烷酮溶液中，磁力搅拌均匀后涂覆在铝箔上，制得正极片； A1. Mix the positive electrode material, conductive carbon black and Li 10 GeP 2 S 12 type sulfide solid electrolyte material, and grind them evenly to obtain positive electrode powder; disperse the positive electrode powder in 4% polyvinylidene fluoride-N-methyl Pyrrolidone solution, magnetically stirred evenly, and then coated on aluminum foil to prepare a positive electrode sheet;
A2、将Li 10GeP 2S 12型硫化物固态电解质材料的粉末放置在压片模具中，压制成固态电解质片，之后将正极片放在固态电解质片的一侧，并加压力压制，最后在固态电解质的另一侧附上锂箔，压制成全固态电池。 A2. Place the powder of Li 10 GeP 2 S 12 type sulfide solid electrolyte material in a tableting mold, press it into a solid electrolyte sheet, then place the positive electrode sheet on one side of the solid electrolyte sheet, press it with pressure, and finally press the Lithium foil is attached to the other side of the solid-state electrolyte and pressed into an all-solid-state battery.
作为本发明的一个实施方案，所述固态电解质片的厚度为200–800μm。As an embodiment of the present invention, the thickness of the solid electrolyte sheet is 200-800 μm.
本发明还涉及一种硫化物基全固态电池，包括正极部分、负极部分和电解质部分；所述正极部分、负极部分、电解质部分中至少一者包括所述的Li 10GeP 2S 12型硫化物固态电解质。 The present invention also relates to a sulfide-based all-solid-state battery, comprising a positive electrode part, a negative electrode part, and an electrolyte part; at least one of the positive electrode part, the negative electrode part, and the electrolyte part includes the Li 10 GeP 2 S 12 type sulfide solid electrolyte.
作为本发明的一个实施方案，所述正极部分由正极活性物质和所述Li 10GeP 2S 12型硫化物固态电解质混合构建，正极活性物质为尖晶石型过渡金属氧化物、具被层状结构的锂过渡金属氧化物、橄榄石、或者这些材料中两种以上的混合物。 As an embodiment of the present invention, the positive electrode part is constructed by mixing the positive electrode active material and the Li 10 GeP 2 S 12 type sulfide solid electrolyte, and the positive electrode active material is a spinel-type transition metal oxide with a layered structure of lithium transition metal oxides, olivine, or a mixture of two or more of these materials.
作为本发明的一个实施方案，所述正极部分中的Li 10GeP 2S 12型硫化物固态电解质的重量占正极部分总重量的百分比为0～40wt％。 As an embodiment of the present invention, the weight percentage of the Li 10 GeP 2 S 12 type sulfide solid electrolyte in the positive electrode part to the total weight of the positive electrode part is 0-40wt%.
作为本发明的一个实施方案，所述正极活性物质为LiCoO 2、LiFePO 4、LiNi xCo yMn 1 -x-yO 2、LiNi xCo yAl 1-x-yO 2、LiNi 0.5Mn 1.5O 4、LiFe xMn 1-xPO 4中的一种或两种以上的混合物。 As an embodiment of the present invention, the positive electrode active material is LiCoO 2 , LiFePO 4 , LiNix Co y Mn 1 -xy O 2 , LiNi x Co y Al 1-xy O 2 , LiNi 0.5 Mn 1.5 O 4 , LiFe One of x Mn 1-x PO 4 or a mixture of two or more.
作为本发明的一个实施方案，所述负极部分由负极活性物质和所述Li 10GeP 2S 12型硫化物固态电解质混合构建，负极活性物质为碳系列材料、含Si碳系材料或橄榄石结构过渡金属材料；所述碳系列材料为人造石墨、天然石墨、硬碳或石墨烯；所述橄榄石结构过渡金属材料为Li 4Ti 5O 12或LiNbTi 2O 7。 As an embodiment of the present invention, the negative electrode part is constructed by mixing the negative electrode active material and the Li 10 GeP 2 S 12 type sulfide solid electrolyte, and the negative electrode active material is a carbon series material, a Si-containing carbon material or an olivine structure Transition metal material; the carbon series material is artificial graphite, natural graphite, hard carbon or graphene; the transition metal material with olivine structure is Li 4 Ti 5 O 12 or LiNbTi 2 O 7 .
作为本发明的一个实施方案，所述负极部分中的Li 10GeP 2S 12型硫化物固态电解质的重量占负极部分总重量的百分比为0～40wt％。 As an embodiment of the present invention, the weight percentage of the Li 10 GeP 2 S 12 type sulfide solid electrolyte in the negative electrode part to the total weight of the negative electrode part is 0-40wt%.
本发明还涉及一种全固态电池制备方法；首先制备正极材料，将电极材料，导电炭黑以及硫化物固态电解质材料按照一定的比例(如，2-3:1:5-6)混合；将其研磨后研磨混合均匀得到正极粉末；将正极粉末分散于4％的聚偏氟乙烯-N-甲基吡咯烷酮溶液中，磁力搅拌均匀后涂覆在铝箔上，制得正极片。正极复合硫化物电解质的原因是为了提高离子电导率。The present invention also relates to a method for preparing an all-solid-state battery; first, the positive electrode material is prepared, and the electrode material, conductive carbon black and sulfide solid electrolyte material are mixed according to a certain ratio (such as, 2-3:1:5-6); Grinding and mixing uniformly to obtain positive electrode powder; dispersing the positive electrode powder in 4% polyvinylidene fluoride-N-methylpyrrolidone solution, stirring evenly by magnetic force, and coating on aluminum foil to obtain positive electrode sheet. The reason for the positive composite sulfide electrolyte is to improve the ionic conductivity.
其次，将硫化物固态电解质材料粉末放置在压片模具中，压制成固态电解质片，之 后将正极片放在固态电解质的一侧，并加压力压制，最后在固态电解质的另一侧附上锂箔，压制成三明治结构的全固态电池。Secondly, the sulfide solid electrolyte material powder is placed in a tablet mold and pressed into a solid electrolyte sheet, then the positive electrode sheet is placed on one side of the solid electrolyte, and pressed with pressure, and finally the lithium battery is attached to the other side of the solid electrolyte. Foil, pressed into an all-solid-state battery in a sandwich structure.
附图说明Description of drawings
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：Other characteristics, objects and advantages of the present invention will become more apparent by reading the detailed description of non-limiting embodiments made with reference to the following drawings:
图1为根据实施例1所制备的Li 10InP 2S 12硫化物固态电解质的XRD图； Fig. 1 is the XRD pattern of the Li 10 InP 2 S 12 sulfide solid state electrolyte prepared according to Example 1;
图2为根据实施例1所制备的全固态电池的循环性能；Fig. 2 is the cycle performance of the all-solid-state battery prepared according to Example 1;
图3为根据实施例1所制备的全固态电池首次充放电曲线图；Fig. 3 is the first charge and discharge curve of the all-solid-state battery prepared according to Example 1;
图4为根据实施例1-4和对比例1-3所制备的电解质的电导率曲线；其中，(A)为以所制备电解质组装的不锈钢对称电池的阻抗谱；(B)为计算得到的所制备电解质的锂离子电导率；Fig. 4 is the conductivity curve of the electrolyte prepared according to Examples 1-4 and Comparative Examples 1-3; Wherein, (A) is the impedance spectrum of the stainless steel symmetric cell assembled with the prepared electrolyte; (B) is calculated The lithium ion conductivity of the prepared electrolyte;
图5为根据实施例1-4和对比例1-3所制备的全固态电池的第50圈充放电曲线图。Fig. 5 is a charge-discharge curve of the 50th cycle of the all-solid-state battery prepared according to Examples 1-4 and Comparative Examples 1-3.
具体实施方式Detailed ways
下面结合实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干调整和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with examples. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make some adjustments and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
实施例1Example 1
本实施例涉及Li 10InP 2S 12硫化物固态电解质及其全固态电池制备；包括如下步骤： This example relates to the preparation of Li 10 InP 2 S 12 sulfide solid electrolyte and its all-solid-state battery; including the following steps:
(1)确定M是In，将适量摩尔比的Li 2S、P 2S 5和掺杂物In 2S 3混合并高能行星球磨，高能行星球磨的转速和时间是500rpm和48h，从而得到初始固态电解质材料。 (1) Determine that M is In, mix Li 2 S, P 2 S 5 and dopant In 2 S 3 in an appropriate molar ratio and perform high-energy planetary ball milling. The speed and time of high-energy planetary ball milling are 500rpm and 48h, thereby obtaining the initial solid electrolyte material.
(2)将步骤(1)得到的粉末40mg放置于12mm直径的压片模具中，在600MPa压制成固态电解质片。(2) Place 40 mg of the powder obtained in step (1) in a tableting mold with a diameter of 12 mm, and press at 600 MPa to form a solid electrolyte tablet.
(3)将步骤(2)得到的片状电解质在氩气的氛围下放入石英管中，并真空封管(～10 –4Pa)。 (3) Put the sheet-shaped electrolyte obtained in step (2) into a quartz tube under an argon atmosphere, and vacuum seal the tube (~10 −4 Pa).
(4)将步骤(3)所得的固态电解质片在550℃热处理12h，得到硫化物固态电解质材料。(4) heat-treating the solid electrolyte sheet obtained in step (3) at 550° C. for 12 hours to obtain a sulfide solid electrolyte material.
(5)将步骤(4)所得的112mg硫化物固态电解质材料、48mg磷酸铁锂和20mg导电炭黑以混合，将其研磨均匀后得到正极粉末。将正极粉末溶解于500mg的4％的聚偏氟乙烯-N-甲基吡咯烷酮溶液中，磁力搅拌均匀后涂覆在铝箔上。(5) Mix 112mg of the sulfide solid electrolyte material obtained in step (4), 48mg of lithium iron phosphate and 20mg of conductive carbon black, and grind them evenly to obtain positive electrode powder. The positive electrode powder was dissolved in 500 mg of 4% polyvinylidene fluoride-N-methylpyrrolidone solution, stirred evenly by magnetic force, and coated on an aluminum foil.
(6)将硫化物固态电解质材料的粉末放置在压片模具中，压制成厚度为500微米左右的固态电解质片，之后将正极片放在固态电解质的一侧，并加压力压制，最后在固态电解质的另一侧附上锂箔，压制成全固态电池。(6) Place the powder of the sulfide solid electrolyte material in a tablet mold, press it into a solid electrolyte sheet with a thickness of about 500 microns, then place the positive electrode sheet on one side of the solid electrolyte, and press it with pressure, and finally in the solid state Lithium foil is attached to the other side of the electrolyte and pressed into an all-solid-state battery.
实施例2Example 2
添加掺杂物Al 2S 3，其余同实施例1。 Dopant Al 2 S 3 is added, and the rest is the same as in Example 1.
实施例3Example 3
掺杂Ga 2S 3，其余同实施例1。 Doped with Ga 2 S 3 , the rest are the same as in Example 1.
实施例4Example 4
掺杂Ta 2S 3，其余同实施例1。 Doped with Ta 2 S 3 , the rest are the same as in Example 1.
对比例1Comparative example 1
本对比例涉及Li 10SiP 2S 12硫化物固态电解质及其制备；包括如下步骤： This comparative example relates to Li 10 SiP 2 S 12 sulfide solid electrolyte and its preparation; including the following steps:
(1)将Li 2S、P 2S 5和掺杂物SiS 2混合并高能行星球磨，高能行星球磨的转速和时间是550rpm和48h，从而得到初始固态电解质材料。 (1) Li 2 S, P 2 S 5 and dopant SiS 2 were mixed and subjected to high-energy planetary ball milling. The rotational speed and time of high-energy planetary ball milling were 550rpm and 48h, so as to obtain the initial solid electrolyte material.
(2)将步骤(1)得到的固态电解质初料40mg放置于12mm直径的压片模具中，在600MPa压制成固态电解质片。(2) Place 40 mg of the solid electrolyte raw material obtained in step (1) in a tableting mold with a diameter of 12 mm, and press at 600 MPa to form a solid electrolyte tablet.
(3)将步骤(2)得到的片状电解质在氩气的氛围下放入石英管中，并真空封管(～10 –4Pa)； (3) Put the sheet electrolyte obtained in step (2) into a quartz tube under an argon atmosphere, and vacuum seal the tube (~10 -4 Pa);
(4)将步骤(3)所得的固态电解质片在550℃热处理24h，得到硫化物固态电解质材料。(4) heat-treating the solid electrolyte sheet obtained in step (3) at 550° C. for 24 hours to obtain a sulfide solid electrolyte material.
(5)将步骤(4)所得的112mg硫化物固态电解质材料、48mg磷酸铁锂和20mg导电炭黑以混合，将其研磨均匀后得到正极粉末。将正极粉末溶解于500mg的4％的聚偏氟乙烯-N-甲基吡咯烷酮溶液中，磁力搅拌均匀后涂覆在铝箔上。(5) Mix 112mg of the sulfide solid electrolyte material obtained in step (4), 48mg of lithium iron phosphate and 20mg of conductive carbon black, and grind them evenly to obtain positive electrode powder. The positive electrode powder was dissolved in 500 mg of 4% polyvinylidene fluoride-N-methylpyrrolidone solution, stirred evenly by magnetic force, and coated on an aluminum foil.
(6)将硫化物固态电解质材料的粉末放置在压片模具中，压制成厚度为500微米左右的固态电解质片，之后将正极片放在固态电解质的一侧，并加压力压制，最后在固态电解质的另一侧附上锂箔，压制成全固态电池。(6) Place the powder of the sulfide solid electrolyte material in a tablet mold, press it into a solid electrolyte sheet with a thickness of about 500 microns, then place the positive electrode sheet on one side of the solid electrolyte, and press it with pressure, and finally in the solid state Lithium foil is attached to the other side of the electrolyte and pressed into an all-solid-state battery.
对比例2Comparative example 2
掺杂SnS 2，其余同对比例1。 Doped with SnS 2 , the rest is the same as Comparative Example 1.
对比例3Comparative example 3
掺杂GeS 2，其余同对比例1。 Doped with GeS 2 , the rest is the same as Comparative Example 1.
性能测试Performance Testing
将上述实施例1～4以及对比例1～3制成的全固态电池在手套箱中装置于专门的电池测试装置中测试电池性能，同时将组装好的电池进行0.5C恒流电池充放电测试，充放电区间为2–4.2V，测试温度为25℃环境的室温中。The all-solid-state batteries made in the above-mentioned Examples 1-4 and Comparative Examples 1-3 were installed in a special battery testing device in a glove box to test the battery performance, and at the same time, the assembled battery was subjected to a 0.5C constant current battery charge and discharge test , the charge and discharge range is 2–4.2V, and the test temperature is at room temperature in a 25°C environment.
将实施例1中制备得到的硫化物固态电解质对其进行XRD测试，测试结果如图1。实施例1制成的全固态电池为2032型号的纽扣电池，电池在0.5C下进行恒电流充放电测试，充放电电压区间为2–4.2V，测试温度为25℃，充放电循环如图3，首次充放电曲线如图2。进一步的，对比实施例1-4和对比例1-3所制备的电解质的电导率曲线(图4)，各电解质的电导率如表1所示。对比实施例1-4和对比例1-3所制备的全固态电池的第50圈充放电曲线图(图5)；由图5可知，相同测试条件下，实施例1中电池具有最高的容量。且从实施例1至对比例3，容量依次下降，这与电导率测试结果一致。The sulfide solid electrolyte prepared in Example 1 was subjected to XRD test, and the test results are shown in Fig. 1 . The all-solid-state battery made in Example 1 is a 2032-type button battery. The battery is subjected to a constant current charge and discharge test at 0.5C. The charge and discharge voltage range is 2–4.2V, and the test temperature is 25°C. The charge and discharge cycle is shown in Figure 3 , the first charge and discharge curve is shown in Figure 2. Further, comparing the conductivity curves of the electrolytes prepared in Examples 1-4 and Comparative Examples 1-3 ( FIG. 4 ), the conductivity of each electrolyte is shown in Table 1. The 50th cycle charge and discharge curve (Fig. 5) of the all-solid-state battery prepared by comparative examples 1-4 and comparative examples 1-3; as can be seen from Fig. 5, under the same test conditions, the battery in embodiment 1 has the highest capacity . And from Example 1 to Comparative Example 3, the capacity decreases sequentially, which is consistent with the conductivity test results.
表1根据实施例1-4和对比例1-3所制备的电解质的电导率。Table 1 The conductivity of the electrolytes prepared according to Examples 1-4 and Comparative Examples 1-3.
电解质electrolyte 电导率mS/cm 2 Conductivity mS/cm 2
实施例1Example 1 11.311.3
实施例2Example 2 6.76.7
实施例3Example 3 3.73.7
实施例4Example 4 1.841.84
对比例1Comparative example 1 0.260.26
对比例2Comparative example 2 0.330.33
对比例3Comparative example 3 0.290.29
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)所制备的硫化物固态电解质材料具有较好的化学稳定性；(1) The prepared sulfide solid electrolyte material has good chemical stability;
(3)将所制的固态电解质应用于全固态电池，提高了电池的循环稳定性；(3) Applying the prepared solid-state electrolyte to an all-solid-state battery improves the cycle stability of the battery;
(4)制备正极时引入硫化物固态电解质，提高了电池整体电化学性能；(4) The introduction of a sulfide solid electrolyte when preparing the positive electrode improves the overall electrochemical performance of the battery;
(5)制备的硫化物电解质所需原料的成本较低，有利于推进大规模的工业生产。(5) The cost of raw materials required for the prepared sulfide electrolyte is low, which is conducive to promoting large-scale industrial production.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art may make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims (8)

  1. 一种Li 10GeP 2S 12型硫化物固态电解质，其特征在于，其化学通式为Li aM bP cS d，其中，M为Al、Ga、In、Ta中的一种或多种，a,b,c,d>0。 A Li 10 GeP 2 S 12 type sulfide solid electrolyte, characterized in that its general chemical formula is Li a M b P c S d , wherein M is one or more of Al, Ga, In, Ta ，a,b,c,d>0.
  2. 根据权利要求1所述的Li 10GeP 2S 12型硫化物固态电解质，其特征在于，所述固态电解质的原料包含以下成分： The Li 10 GeP 2 S 12 type sulfide solid electrolyte according to claim 1, wherein the raw material of the solid electrolyte comprises the following components:
    Li源：LiH、Li 2S 2、Li 2S中的一种或多种组合物； Li source: one or more combinations of LiH, Li 2 S 2 , Li 2 S;
    S源：S、H 2S、P 2S 5、P 4S 9、P 4S 3、Li 2S 2、Li 2S、M 2S 3中的一种或多种组合物； S source: one or more combinations of S, H 2 S, P 2 S 5 , P 4 S 9 , P 4 S 3 , Li 2 S 2 , Li 2 S, M 2 S 3 ;
    P源：P、P 2S 5、P 4S 9、P 4S 3、P 4S 6、P 4S 5中的一种或多种组合物； P source: one or more combinations of P, P 2 S 5 , P 4 S 9 , P 4 S 3 , P 4 S 6 , P 4 S 5 ;
    M源为：In 2S 2、In 2S 3、Al 2S 3、Ga 2S 3、Ta 2S 3中的一种或多种组合物。 The M source is: one or more combinations of In 2 S 2 , In 2 S 3 , Al 2 S 3 , Ga 2 S 3 , and Ta 2 S 3 .
  3. 根据权利要求1所述的Li 10GeP 2S 12型硫化物固态电解质，其特征在于，所述固态电解质中Li与M的质量比为2-10:1。 The Li 10 GeP 2 S 12 type sulfide solid electrolyte according to claim 1, characterized in that the mass ratio of Li to M in the solid electrolyte is 2-10:1.
  4. 一种根据权利要求1～3中任一项所述的Li 10GeP 2S 12型硫化物固态电解质的制备方法，其特征在于，所述包括如下步骤： A method for preparing the Li 10 GeP 2 S 12 type sulfide solid electrolyte according to any one of claims 1 to 3, characterized in that the method comprises the following steps:
    S1、将Li、S、P、M源混合球磨，得到初始固态电解质粉末，所述球磨的转速为500–650rpm，球磨时间为12–60h；S1. Mix and ball-mill Li, S, P, and M sources to obtain initial solid electrolyte powder. The speed of the ball mill is 500-650rpm, and the ball-milling time is 12-60h;
    S2、将步骤S1得到的初始固态电解质粉末，在300–900MPa下压片，得到初始固态电解质片；S2. Compressing the initial solid electrolyte powder obtained in step S1 under 300-900 MPa to obtain an initial solid electrolyte sheet;
    S3、将步骤S2得到的初始固态电解质片密封在石英管或玻璃管中，并真空封管(～10 –4Pa)，煅烧温度500–650℃，时间12–60h，得到硫化物固态电解质材料。 S3. Seal the initial solid electrolyte sheet obtained in step S2 in a quartz tube or glass tube, and vacuum seal the tube (~ 10-4 Pa), calcining at a temperature of 500-650°C for 12-60 hours to obtain a sulfide solid electrolyte material .
  5. 一种根据权利要求1～3中任一项所述的Li 10GeP 2S 12型硫化物固态电解质在制备全固态电池中的应用。 An application of the Li 10 GeP 2 S 12 type sulfide solid electrolyte according to any one of claims 1 to 3 in the preparation of an all-solid-state battery.
  6. 根据权利要求6所述的应用，其特征在于，具体包括：The application according to claim 6, characterized in that it specifically comprises:
    A1、将正极材料、导电炭黑以及Li 10GeP 2S 12型硫化物固态电解质材料混合，将其研磨均匀后得到正极粉末；将正极粉末分散于4％的聚偏氟乙烯-N-甲基吡咯烷酮溶液中，磁力搅拌均匀后涂覆在铝箔上，制得正极片； A1. Mix the positive electrode material, conductive carbon black and Li 10 GeP 2 S 12 type sulfide solid electrolyte material, and grind them evenly to obtain positive electrode powder; disperse the positive electrode powder in 4% polyvinylidene fluoride-N-methyl Pyrrolidone solution, magnetically stirred evenly, and then coated on aluminum foil to prepare a positive electrode sheet;
    A2、将Li 10GeP 2S 12型硫化物固态电解质材料的粉末放置在压片模具中，压制成固态电解质片，之后将正极片放在固态电解质片的一侧，并加压力压制，最后在固态电解质的另一侧附上锂箔，压制成全固态电池。 A2. Place the powder of Li 10 GeP 2 S 12 type sulfide solid electrolyte material in a tableting mold, press it into a solid electrolyte sheet, then place the positive electrode sheet on one side of the solid electrolyte sheet, press it with pressure, and finally press the Lithium foil is attached to the other side of the solid-state electrolyte and pressed into an all-solid-state battery.
  7. 根据权利要求7所述的应用，其特征在于，所述固态电解质片的厚度为200–800μm。The application according to claim 7, characterized in that the thickness of the solid electrolyte sheet is 200-800 μm.
  8. 根据权利要求10所述的硫化物基全固态电池，其特征在于，所述正极活性物质为LiCoO 2、LiFePO 4、LiNi xCo yMn 1-x-yO 2、LiNi xCo yAl 1-x-yO 2、LiNi 0.5Mn 1.5O 4、LiFe xMn 1 -xPO 4中的一种或两种以上的混合物。 The sulfide-based all-solid-state battery according to claim 10, wherein the positive electrode active material is LiCoO 2 , LiFePO 4 , LiNi x Co y Mn 1-xy O 2 , LiNi x Co y Al 1-xy O 2. One or a mixture of two or more of LiNi 0.5 Mn 1.5 O 4 , LiF x Mn 1 -x PO 4 .
PCT/CN2022/113370 2021-09-01 2022-08-18 Method for preparing sulfide solid electrolyte material and application thereof WO2023030026A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111021844.0 2021-09-01
CN202111021844.0A CN113948764A (en) 2021-09-01 2021-09-01 Preparation method and application of sulfide solid electrolyte material

Publications (1)

Publication Number Publication Date
WO2023030026A1 true WO2023030026A1 (en) 2023-03-09

Family

ID=79327637

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/113370 WO2023030026A1 (en) 2021-09-01 2022-08-18 Method for preparing sulfide solid electrolyte material and application thereof

Country Status (2)

Country Link
CN (1) CN113948764A (en)
WO (1) WO2023030026A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113948764A (en) * 2021-09-01 2022-01-18 上海屹锂新能源科技有限公司 Preparation method and application of sulfide solid electrolyte material
CN114789993B (en) * 2022-05-05 2024-01-30 上海屹锂新能源科技有限公司 Modified sulfur silver germanium mineral solid electrolyte and preparation method and application thereof
CN114899480A (en) * 2022-05-13 2022-08-12 上海屹锂新能源科技有限公司 Sulfide-doped solid electrolyte and preparation method and application thereof
CN115304377A (en) * 2022-09-14 2022-11-08 吉林师范大学 LGPS ceramic chip, preparation method thereof and pressing die of LGPS ceramic chip

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013033659A (en) * 2011-08-02 2013-02-14 Toyota Motor Corp Solid electrolyte material-containing body and battery
CN103401018A (en) * 2013-08-09 2013-11-20 宁德时代新能源科技有限公司 Solid-state electrolyte material of lithium ion battery
CN109361019A (en) * 2018-09-15 2019-02-19 中国科学院青岛生物能源与过程研究所 A kind of all solid state lithium metal battery and its chemical property improvement method
JP2019125502A (en) * 2018-01-17 2019-07-25 トヨタ自動車株式会社 Sulfide solid electrolyte
CN113948764A (en) * 2021-09-01 2022-01-18 上海屹锂新能源科技有限公司 Preparation method and application of sulfide solid electrolyte material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013033659A (en) * 2011-08-02 2013-02-14 Toyota Motor Corp Solid electrolyte material-containing body and battery
CN103401018A (en) * 2013-08-09 2013-11-20 宁德时代新能源科技有限公司 Solid-state electrolyte material of lithium ion battery
JP2019125502A (en) * 2018-01-17 2019-07-25 トヨタ自動車株式会社 Sulfide solid electrolyte
CN109361019A (en) * 2018-09-15 2019-02-19 中国科学院青岛生物能源与过程研究所 A kind of all solid state lithium metal battery and its chemical property improvement method
CN113948764A (en) * 2021-09-01 2022-01-18 上海屹锂新能源科技有限公司 Preparation method and application of sulfide solid electrolyte material

Also Published As

Publication number Publication date
CN113948764A (en) 2022-01-18

Similar Documents

Publication Publication Date Title
WO2023030026A1 (en) Method for preparing sulfide solid electrolyte material and application thereof
CN100470894C (en) Preparation method of phosphorus position partly substituted iron lithium phosphate powder
CN106298250B (en) A kind of solid lithium ion-super capacitor hybrid battery
CN106328992B (en) A kind of preparation method of lithium ion battery and the lithium ion battery
WO2020098427A1 (en) Lithium ion battery negative electrode material and non-aqueous electrolyte battery
WO2020073915A1 (en) Lithium ion battery negative electrode material and non-aqueous electrolyte battery
CN101964412B (en) Lithium iron phosphate/carbon composite material with surface modified by coupling agent and preparation method thereof
WO2023030025A1 (en) Preparation method for argyrodite-type solid electrolyte, and all-solid-state battery application thereof
CN110380133A (en) A kind of transition zone design method of inorganic solid electrolyte and positive interpolar
CN106450214B (en) Layered lithium iron phosphate composite material and preparation method thereof
WO2016176928A1 (en) Negative electrode material, preparation method therefor, and lithium-ion secondary battery using the negative electrode material
CN102034971A (en) Lithium-ion battery lithium iron phosphate/polypyrrole pyridine composite anode material and preparation method thereof
CN114789993B (en) Modified sulfur silver germanium mineral solid electrolyte and preparation method and application thereof
CN107204426A (en) A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property
CN107452950A (en) The anode material for lithium-ion batteries and method of a kind of stable circulation
CN103094567A (en) Anode material of lithium fast ionic conductor compounded lithium battery and preparation method of anode material
Chang et al. Study on synthesis of spinel LiNi0. 5Mn1. 5O4 cathode material and its electrochemical properties by two‐stage roasting
CN111313010A (en) Preparation method of high-capacity lithium ion battery anode material lithium iron phosphate
CN107293723A (en) A kind of binder free Na3V2(PO4)3/ C composite lithium ion battery anodes and preparation method thereof
CN111247673A (en) Composition for forming active material layer, method for producing same, electrode sheet for all-solid-state secondary battery, and method for producing all-solid-state secondary battery
CN113629242A (en) Preparation method of polyanionic vanadium iron sodium phosphate positive electrode material
WO2014073466A1 (en) Positive electrode material, all-solid-state battery, and method for producing positive electrode material and all-solid-state battery
CN115312833B (en) All-solid-state battery based on rare earth halide solid electrolyte and preparation method thereof
CN114447423B (en) Sulfide solid electrolyte with lithium supplementing and moisture absorbing effects
Tian et al. A new lithium‐rich layer‐structured cathode material with improved electrochemical performance and voltage maintenance

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22863166

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE