WO2019129267A1 - 反钙钛矿型固态电解质及合成方法、电池、车辆 - Google Patents

反钙钛矿型固态电解质及合成方法、电池、车辆 Download PDF

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WO2019129267A1
WO2019129267A1 PCT/CN2018/125423 CN2018125423W WO2019129267A1 WO 2019129267 A1 WO2019129267 A1 WO 2019129267A1 CN 2018125423 W CN2018125423 W CN 2018125423W WO 2019129267 A1 WO2019129267 A1 WO 2019129267A1
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solid electrolyte
perovskite
ball
present application
ball mill
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French (fr)
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布库尔克劳迪乌•博格丹
杨红新
马忠龙
王格日乐图
庞瑞君
谭宏亮
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Great Wall Motor Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • 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
    • H01M10/056—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • 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 application relates to the field of electrochemistry, and in particular to an anti-perovskite type solid electrolyte and a synthesis method, a battery, and a vehicle.
  • a battery based on a liquid electrolyte system even if it has high conductivity and excellent electrode surface wettability, has poor electrochemical performance and thermal stability, low ion selectivity, and poor safety.
  • Solid electrolytes can overcome the long-lasting problems of liquid electrolytes and offer the possibility of developing new chemical batteries. Based on these advantages, the research use of solid electrolyte batteries has shown a rapid growth trend. At present, the anti-perovskite material is a promising inorganic crystalline solid electrolyte material, which has been closely watched by many researchers and businesses.
  • the methods for synthesizing an anti-perovskite-type solid electrolyte mainly include a solid state synthesis method, a hydrothermal synthesis method, and a vacuum deposition method.
  • the solid state synthesis method needs to be carried out at a temperature higher than 400 ° C
  • the hydrothermal synthesis method needs to be carried out at a temperature higher than 230 ° C.
  • the vacuum deposition method needs to deposit the starting materials on the substrate in a vacuum environment, Therefore, the current method for synthesizing an anti-perovskite solid electrolyte has high energy consumption and complicated process, and thus the production cost of the anti-perovskite solid electrolyte is high.
  • This application is intended to alleviate or solve at least one of the above mentioned problems at least to some extent.
  • the present application proposes a method of synthesizing an anti-perovskite solid electrolyte.
  • the anti-perovskite-type solid electrolyte includes Li 3 OX, the X is a halogen element, and the method includes: placing LiOH and LiX in a ball mill tank for ball milling treatment to obtain the Anti-perovskite solid electrolyte.
  • the synthesis process of the anti-perovskite solid electrolyte can be simplified, the anti-perovskite solid electrolyte having excellent performance can be obtained, and the ball milling treatment does not require heating, thereby reducing energy consumption and reducing the anti-perovskite solid electrolyte. Production costs.
  • the X is Cl, Br or I.
  • the X is Cl.
  • Li 3 OCl can be prepared by a ball milling process to obtain a Li 3 OCl type solid dielectric.
  • the method further comprises: mixing a dopant with LiOH and LiX, and placing the ball in a ball mill for ball milling, the dopant comprising at least one of Na, Mg, and Al elements .
  • the anti-perovskite type solid electrolyte can be applied to various environments.
  • the method further comprises: ball milling, Ba(OH) 2 .8H 2 O, and water are placed in the ball mill jar for ball milling.
  • a powder such as LiOH or LiX can be subjected to a preferable ball milling treatment to obtain an anti-perovskite-type solid electrolyte excellent in performance.
  • the ball mill tank is a zirconia ball mill tank, and the ball mill ball is a zirconia ball.
  • the zirconia ball mill has high hardness, high strength, high toughness, high wear resistance and chemical corrosion resistance. The ball milling treatment effect is good.
  • the zirconia ball can be used as a ball grinding ball without introducing impurities to ensure the final formation of anti-calcium titanium. The purity of the mineral solid electrolyte.
  • the mass ratio of the LiOH, LiX, Ba(OH) 2 .8H 2 O, and water is 30:30:1:50.
  • the zirconia balls have a diameter of 1.5 to 5 mm. Thereby, it can be ensured that the zirconia ball has a good ball grinding effect on powders such as LiOH and LiX.
  • the volume of the ball mill tank is 40-60 ml.
  • the rotational speed of the ball milling process is 300-550 rpm. Therefore, the efficiency and effect of the ball milling can be further improved.
  • the ball milling treatment time is 4-6 h.
  • the present application proposes an anti-perovskite solid electrolyte.
  • the anti-perovskite type solid electrolyte is formed by the method described above, whereby the anti-perovskite type solid electrolyte has excellent performance and is low in cost.
  • no free H + is present in the anti-perovskite solid electrolyte.
  • the battery formed of the anti-perovskite type solid electrolyte can have excellent use properties.
  • the inverse perovskite-type solid electrolyte has a glass transition temperature of less than 150 °C. Therefore, the battery formed of the anti-perovskite type solid electrolyte can have excellent use properties.
  • the application proposes a battery.
  • the battery includes the above-described anti-perovskite-type solid electrolyte, and thus, the battery has all the features and advantages of the foregoing anti-perovskite-type solid electrolyte, and details are not described herein again. .
  • the battery has excellent performance and low cost.
  • the application proposes a vehicle.
  • the vehicle includes the battery described above, whereby the vehicle has all of the features and advantages of the battery described above, and details are not described herein.
  • the vehicle has a lower cost and a longer service life.
  • Figure 2 shows an enlarged view of a partial area of Figure 1;
  • FIG. 3 shows an H NMR spectrum of an anti-perovskite solid electrolyte according to an embodiment of the present application
  • Figure 5 shows the voltage of a battery in accordance with one embodiment of the present application.
  • the present application proposes a method for synthesizing an anti-perovskite solid electrolyte.
  • the anti-perovskite-type solid electrolyte includes Li 3 OX, and X is a halogen element.
  • the anti-perovskite-type solid electrolyte may be Li 3 OF, Li 3 OCl, or Li 3 OBr.
  • the method comprises: placing LiOH and LiX in a ball mill tank for ball milling treatment to obtain the inverse perovskite-type solid electrolyte.
  • the synthesis process of the anti-perovskite solid electrolyte can be simplified, the anti-perovskite solid electrolyte having excellent performance can be obtained, and the ball milling treatment does not require heating, thereby reducing energy consumption and reducing the anti-perovskite solid electrolyte. Production costs.
  • the content of free H + is extremely small, and can be directly used for preparing a lithium ion battery without high temperature drying treatment, thereby preventing the high temperature drying treatment from affecting the anti-perovskite.
  • the glass transition temperature of a solid electrolyte is extremely small, and can be directly used for preparing a lithium ion battery without high temperature drying treatment, thereby preventing the high temperature drying treatment from affecting the anti-perovskite.
  • the anti-perovskite material is a promising inorganic crystalline solid electrolyte material with a low glass transition temperature, which can make the battery composed of the anti-perovskite electrode active material have good performance. Electrical conductivity, safety and low cost.
  • anti-perovskite materials have attracted the attention of many researchers and businesses.
  • Current methods for synthesizing anti-perovskite-type solid electrolytes include solid state synthesis, hydrothermal synthesis, and vacuum deposition.
  • the solid state synthesis method needs to be carried out at a temperature higher than 400 ° C, and the hydrothermal synthesis method needs to be carried out at a temperature higher than 230 ° C.
  • the vacuum deposition method needs to deposit the starting materials on the substrate in a vacuum environment. High consumption and complicated process lead to high production cost of anti-perovskite solid electrolyte.
  • a raw material (a powder such as LiOH and LiX) is reacted by a ball milling treatment without a high-temperature heat treatment, thereby obtaining an anti-perovskite solid state having a lower glass transition temperature.
  • Electrolyte the ball milling process does not require heating, so that energy consumption in the preparation process of the anti-perovskite solid electrolyte can be reduced, and the production cost can be reduced.
  • the ball milling process is simple, easy to operate, and can be mass-produced, thereby further reducing production costs.
  • the reaction can be carried out by placing a powder such as LiOH and LiX in a ball mill tank, and the reaction can be specifically performed as follows:
  • the Li 3 OX formed after the ball milling treatment has a lower glass transition temperature. According to the synthesis method of the embodiment of the present application, heating is not required, the process is simple, mass production can be realized, and the production cost of the anti-perovskite solid electrolyte can also be reduced.
  • the LiX in the starting material forming the anti-perovskite solid electrolyte may be LiF, LiCl or LiBr, whereby the anti-perovskite solid electrolyte synthesized by the method may be Li 3 OF, Li 3 OCl or Li 3 OBr.
  • the anti-perovskite solid electrolyte may be Li 3 OCl.
  • a certain amount of Ba(OH) 2 .8H 2 O and water may be placed in a ball mill tank to mix Ba(OH) 2 ⁇ 8H 2 O and water with LiOH and LiX. After ball milling, a relatively pure Li 3 OX can be obtained.
  • the mass ratio of LiOH, LiX, Ba(OH) 2 .8H 2 O, and water may be 30:30:1:50.
  • the dopant in order to adapt the anti-perovskite solid electrolyte synthesized by the method to more application environments, the dopant may be mixed with LiOH, LiX, etc., and placed in a ball mill tank for ball milling. Treatment to obtain an anti-perovskite solid electrolyte that can accommodate more environments.
  • the dopant may include at least one of Na, Mg, and Al elements.
  • a salt substance containing Na+ or Mg 2+ or Al 3+ may be mixed with LiOH, LiX or the like.
  • the ball mill ball needs to be placed in the ball mill tank together with the starting material, and then the ball mill tank containing the ball mill ball and the starting material is placed in a ball mill for ball milling.
  • the specific type of the ball mill can is not particularly limited, and those skilled in the art can design according to specific conditions.
  • the ball mill tank used in the method may be a zirconia ball mill tank, and the zirconia ball mill tank has high hardness, high strength, high toughness, high wear resistance, chemical resistance, and ball mill treatment. The effect is good.
  • the ball grinding ball used in the method may be a zirconia ball, the zirconia ball has good strength and hardness, and can be combined with a zirconia ball mill to achieve a good ball milling effect, and the zirconia ball can be used. No other impurities are introduced to ensure the purity of the finally formed anti-perovskite solid electrolyte.
  • the zirconia balls may have a diameter of 1.5 to 5 mm. Thereby, it can be ensured that the zirconia ball has a good ball grinding effect on powders such as LiOH and LiX. Applicants have found that if the diameter of the zirconia balls is too large or too small, it will result in insufficient ball milling of the starting materials. According to a particular embodiment of the present application, the zirconia balls may have a diameter of 4 mm.
  • the volume of the ball mill can be 40-60 ml. Thereby, the space for the ball milling treatment can be ensured, and a better ball grinding effect can be obtained. Applicants have found that if the volume of the ball mill can be too large or too small, it will result in insufficient ball milling of the starting material. According to a particular embodiment of the present application, the volume of the ball mill can be 55 ml.
  • the rotational speed of the ball milling process may be 300-550 rpm.
  • a powder such as LiOH or LiX can be reacted to obtain a reverse perovskite-type solid electrolyte having excellent properties.
  • the rotational speed of the ball milling process can be 450 rpm.
  • the time of the ball milling treatment may be 4-6 hours. Thereby, it is possible to allow the powders such as LiOH and LiX to have sufficient time to complete the reaction, and to ensure that the finally obtained anti-perovskite-type solid electrolyte has good performance. Applicants have found that the ball milling process is too short and can result in insufficient reaction of the starting materials. The ball milling treatment takes too long and does not significantly improve the performance of the obtained anti-perovskite material. According to a specific embodiment of the present application, the time of the ball milling treatment may be 5.5 hours.
  • the present application proposes an anti-perovskite solid electrolyte.
  • the anti-perovskite type solid electrolyte is formed by the method described above, whereby the anti-perovskite type solid electrolyte has excellent performance and is low in cost.
  • the anti-perovskite solid electrolyte prepared according to the examples of the present application was analyzed by differential scanning calorimetry (DSC analysis), and referring to FIG. 1, the glass transition of the anti-perovskite solid electrolyte synthesized by the ball milling treatment method was used.
  • the temperature is lower than 150 ° C, and the melting point of the anti-perovskite solid electrolyte is about 270 ° C.
  • the DSC spectrum of the above temperature range is amplified.
  • the anti-perovskite solid electrolyte has two glass transition temperatures.
  • the first glass transition temperature is about 80 ° C
  • the second glass transition temperature is about 115 ° C.
  • the anti-perovskite solid electrolyte synthesized by the ball milling treatment method and the anti-perovskite solid electrolyte synthesized by the solid state synthesis method are analyzed by a nuclear magnetic resonance method to obtain a nuclear magnetic resonance spectrum (HNMR).
  • HNMR nuclear magnetic resonance spectrum
  • the anti-perovskite type solid electrolyte synthesized by the ball milling treatment method does not contain free H +
  • the anti-perovskite type solid electrolyte synthesized by the solid state synthesis method contains free H + .
  • the anti-perovskite type solid electrolyte synthesized by the ball milling treatment method has excellent performance, and the post-treatment process can be omitted, for example, the subsequent removal of the free H + treatment step having a negative influence can be omitted.
  • the anti-perovskite solid electrolyte formed by the ball milling treatment is tested by X-ray diffraction (XRD) at room temperature and 300 ° C, respectively, and the test environment is a nitrogen atmosphere, referring to FIG. 4 .
  • the anti-perovskite-type solid electrolyte has a small amount of hydroxide at room temperature, and the anti-perovskite-type solid electrolyte is substantially amorphous at 300 °C.
  • the anti-perovskite solid electrolyte has a melting point of about 270 ° C.
  • the anti-perovskite solid electrolyte when the anti-perovskite solid electrolyte is heated to 300 ° C, the anti-perovskite solid electrolyte is in a molten state. , showing an amorphous structure.
  • the anti-perovskite type solid electrolyte formed by the ball milling treatment has a lower glass transition temperature, whereby the calcium is lower at a lower temperature (for example, lower than a glass transition temperature)
  • the titanium ore type solid electrolyte has a crystalline structure
  • the anti-perovskite type solid electrolyte has an amorphous structure at a high temperature (for example, higher than a glass transition temperature).
  • the above XRD test data indicates that the anti-perovskite type solid electrolyte material prepared by the method has characteristics similar to those of the anti-perovskite type solid electrolyte prepared by the solid state synthesis method. That is to say, the method can obtain a good performance anti-perovskite type solid electrolyte material by a simple ball milling treatment.
  • the application proposes a battery.
  • the battery includes the reverse perovskite type solid electrolyte described above.
  • the battery may further include a positive electrode and a negative electrode, and a solid electrolyte disposed between the positive electrode and the negative electrode, and the solid electrolyte contains the above-described anti-perovskite material.
  • the positive electrode has a positive active material, and after forming an electrical circuit between the positive electrode and the negative electrode, power can be supplied to an external device.
  • the battery has all of the features and advantages of the anti-perovskite type solid electrolyte described above, and will not be described herein. In general, the battery has excellent performance and low cost.
  • the application proposes a vehicle.
  • the vehicle includes the battery described above, whereby the vehicle has all of the features and advantages of the battery described above, and details are not described herein.
  • the vehicle has a structure of a vehicle body, an electronic system, etc., and the battery can be disposed at a fixed position in the vehicle body, for example, at the bottom of the vehicle body, and connected to an electronic system to utilize the battery to power the vehicle.
  • the vehicle has a lower cost and a longer service life.
  • the anti-perovskite solid electrolyte obtained in Example 1 was made into a solid sheet of 1 mm to prepare a sandwich structure of Li/Li 3 OCl/Li, and subjected to electrochemical impedance spectroscopy (EIS) and voltage stability tests. Electrochemical impedance test, the battery has high conductivity, the conductivity of the battery is not less than 9ms/cm 2 by electrochemical impedance spectroscopy, and the battery has a stable electrochemical window by voltage stability test. Figure 5. It can be seen that the anti-perovskite material prepared by the method has excellent performance and is suitable for use in a lithium ion battery as a solid electrolyte.
  • the description of the terms “one embodiment”, “another embodiment” and the like means that the specific features, structures, materials or characteristics described in connection with the embodiments are included in at least one embodiment of the present application. .
  • the schematic representation of the above terms is not necessarily directed to the same embodiment or example.
  • the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.
  • various embodiments or examples described in the specification, as well as features of various embodiments or examples may be combined and combined.
  • the terms “first” and “second” are used for descriptive purposes only, and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated.

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Abstract

一种反钙钛矿型固态电解质及合成方法、电池、车辆。所述反钙钛矿型固态电解质包括Li 3OX，所述X为卤素元素，所述方法包括：将LiOH以及LiX放入球磨罐中进行球磨处理，以便获得所述反钙钛矿型固态电解质。

Description

反钙钛矿型固态电解质及合成方法、电池、车辆 技术领域
本申请涉及电化学领域，具体地，涉及反钙钛矿型固态电解质及合成方法、电池、车辆。
背景技术
电池在我们生活中的实际应用起着重要的作用，包括电子消费，提供汽车的动力，间歇性可再生能源发电的固定负载等。随着携式电子器件、电动车、网络储能系统等设备的快速发展，要求电池具有更高的能量密度、更长的循环寿命，而且更安全廉价。基于液态电解质系统的电池，即使其具有高导电性和优秀的电极表面润湿性，但其电化学性能和热稳定性欠佳，离子选择性低，安全性差。固态电解质可以克服液态电解质持久的问题，也为开发新的化学电池提供了可能性。基于这些优点，固态电解质电池的研究使用已经出现迅速增长的趋势。目前，反钙钛矿型材料是一种很有潜力的无机晶体固态电解质材料，受到众多研究者以及商家的密切关注。
然而，目前的反钙钛矿型固态电解质及合成方法、电池、车辆仍有待改进。
申请内容
本申请是基于发明人对于以下事实和问题的发现和认识作出的：
申请目前，用于合成反钙钛矿型固态电解质的方法主要有固态合成法、热液合成法以及真空沉积法。其中，固态合成法需要在高于400℃的温度下进行，热液合成法需要在高于230℃的温度下进行，真空沉积法需要将起始原料在真空环境中沉积到基材上，由此，目前用于合成反钙钛矿型固态电解质的方法能耗较高、过程复杂，从而导致反钙钛矿型固态电解质的生产成本较高。
本申请旨在至少一定程度上缓解或解决上述提及问题中至少一个。
在本申请的一个方面，本申请提出了一种合成反钙钛矿型固态电解质的方法。根据本申请的实施例，所述反钙钛矿型固态电解质包括Li 3OX，所述X为卤素元素，所述方法包括：将LiOH以及LiX放入球磨罐中进行球磨处理，以便获得所述反钙钛矿型固态电解质。由此，可以简化反钙钛矿型固态电解质的合成过程，获得具有优良性能的反钙钛矿型固态电解质，且球磨处理不需要加热，进而可以降低能耗，降低反钙钛矿型固态电解质的生产成本。
根据本申请的实施例，所述X为Cl、Br或I。
根据本申请的实施例，所述X为Cl。由此，可以利用球磨过程制备Li 3OCl，获得Li 3OCl 型固态电介质。
根据本申请的实施例，该方法进一步包括：将掺杂剂与LiOH以及LiX混合，并放入所述球磨罐中进行球磨处理，所述掺杂剂包括Na、Mg、Al元素的至少之一。由此，该反钙钛矿型固态电解质可以适用多种环境。
根据本申请的实施例，该方法进一步包括：将球磨球、Ba(OH) 2·8H 2O以及水放入所述球磨罐中进行球磨处理。由此，可以对LiOH以及LiX等粉末进行较好的球磨处理，获得性能优良的反钙钛矿型固态电解质。
根据本申请的实施例，所述球磨罐为氧化锆球磨罐，所述球磨球为氧化锆球。氧化锆球磨罐具有高硬度、高强度、高韧性以及极高的耐磨性、耐化学腐蚀性，球磨处理效果好，利用氧化锆球作球磨球可以不引入杂质，保证最终形成的反钙钛矿型固态电解质的纯度。
根据本申请的实施例，所述LiOH、LiX、Ba(OH) 2·8H 2O以及水的质量比为30:30:1:50。由此，可以获得性能优良的反钙钛矿型固态电解质。
根据本申请的实施例，所述氧化锆球的直径为1.5-5mm。由此，可以保证氧化锆球对LiOH以及LiX等粉末具有较好的球磨效果。
根据本申请的实施例，所述球磨罐的体积为40-60ml。由此，可以保证球磨处理的空间，进而获得较好的球磨效果。
根据本申请的实施例，所述球磨处理的转速为300-550rpm。由此，可以进一步提高球磨的效率以及效果。
根据本申请的实施例，所述球磨处理的时间为4-6h。由此，可以使LiOH以及LiX等粉末有充足的时间完成反应，并保证最终获得的反钙钛矿型固态电解质具有良好的性能。
在本申请的另一方面，本申请提出了一种反钙钛矿型固态电解质。根据本申请的实施例，该反钙钛矿型固态电解质是由前面所述的方法形成的，由此，该反钙钛矿型固态电解质具有优良的性能，且成本较低。
根据本申请的实施例，所述反钙钛矿型固态电解质中无自由H +存在。由此，由该反钙钛矿型固态电解质形成的电池可以具有优良的使用性能。
根据本申请的实施例，反钙钛矿型固态电解质的玻璃化转变温度低于150℃。由此，由该反钙钛矿型固态电解质形成的电池可以具有优良的使用性能。
在本申请的另一方面，本申请提出了一种电池。根据本申请的实施例，该电池包括前面所述的反钙钛矿型固态电解质，由此，该电池具有前面所述的反钙钛矿型固态电解质的全部特征以及优点，在此不再赘述。总的来说，该电池具有优良的使用性能，且成本较低。
在本申请的另一方面，本申请提出了一种车辆。根据本申请的实施例，该车辆包括前面所述的电池，由此，该车辆具有前面所述的电池的全部特征以及优点，在此不再赘述。总的来说，该车辆具有较低的成本以及较长的使用寿命。
附图说明
本申请的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1显示了根据本申请一个实施例的反钙钛矿型固态电解质的DSC图谱；
图2显示了图1中局部区域的放大图；
图3显示了根据本申请一个实施例的反钙钛矿型固态电解质的HNMR图谱；
图4显示了根据本申请一个实施例的反钙钛矿型固态电解质的XRD图谱；以及
图5显示了根据本申请一个实施例的电池的电压。
具体实施方式
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。
在本申请的一个方面，本申请提出了一种反钙钛矿型固态电解质合成方法。根据本申请的实施例，该反钙钛矿型固态电解质包括Li 3OX，X为卤素元素，具体的，该反钙钛矿型固态电解质可以为Li 3OF、Li 3OCl或者Li 3OBr。根据本申请的实施例，该方法包括：将LiOH以及LiX放入球磨罐中进行球磨处理，以便获得该反钙钛矿型固态电解质。由此，可以简化反钙钛矿型固态电解质的合成过程，获得具有优良性能的反钙钛矿型固态电解质，且球磨处理不需要加热，进而可以降低能耗，降低反钙钛矿型固态电解质的生产成本。并且，利用该方法获得的反钙钛矿型固态电解质中，自由H +的含量极少，可不经高温干燥处理，直接用于制备锂离子电池，从而可以避免高温干燥处理影响该反钙钛矿型固态电解质的玻璃化转变温度。
为了便于理解，下面首先对根据本申请实施例的反钙钛矿型固态电解质的合成方法进行简单说明：
如前所述，反钙钛矿型材料是一种很有潜力的无机晶体固态电解质材料，具有较低的玻璃化转变温度，可以使由反钙钛矿型电极活性材料构成的电池具有良好的导电性、安全性以及较低的成本。由此，反钙钛矿型材料受到众多研究者以及商家的关注。目前用于合成反钙钛矿型固态电解质的方法主要有固态合成法、热液合成法以及真空沉积法。固态合成法需要在高于400℃的温度下进行，热液合成法需要在高于230℃的温度下进行，真空沉积法需要将起始原料在真空环境中沉积到基材上，上述工艺能耗高、过程复杂，导致反钙钛矿型固态电解质的生产成本较高。
根据本申请的实施例，采用球磨处理的方法，使起始原料(LiOH以及LiX等粉末)发 生反应，不经过高温加热处理，进而可获得具有较低玻璃化转变温度的反钙钛矿型固态电解质。根据本申请的实施例，球磨处理不需要加热，从而可以降低反钙钛矿型固态电解质制备过程中能量的消耗，降低生产成本。并且，球磨处理工艺简单，操作方便，可以实现大批量生产，从而进一步降低生产成本。
下面根据本申请的具体实施例，对该方法的具体过程进行详细说明：
根据本申请的实施例，通过将LiOH以及LiX等粉末放入球磨罐里进行球磨处理，可以发生反应，具体的可以发生如下反应：
Figure PCTCN2018125423-appb-000001
经过球磨处理后形成的Li 3OX具有较低的玻璃化转变温度。根据本申请实施例的合成方法，不需加热、工艺简单、可实现大批量生产，进而还可以降低反钙钛矿型固态电解质的生产成本。
根据本申请的实施例，形成该反钙钛矿型固态电解质的起始原料中的LiX可以为LiF、LiCl或者LiBr，由此，由该方法合成的反钙钛矿型固态电解质可以为Li 3OF、Li 3OCl或者Li 3OBr。根据本申请的具体实施例，该反钙钛矿型固态电解质可以为Li 3OCl。
根据本申请的实施例，还可以在球磨罐中放入一定量的Ba(OH) 2·8H 2O以及水，使Ba(OH) 2·8H 2O以及水与LiOH以及LiX进行混合，在经过球磨处理后能够获得较为纯净的Li 3OX。根据本申请的实施例，LiOH、LiX、Ba(OH) 2·8H 2O以及水的质量比可以为30:30:1:50。由此，可以使上述物质充分反应生成Li 3OX，得到较为纯净的反钙钛矿型固态电解质。
根据本申请的实施例，为了使由该方法合成的反钙钛矿型固态电解质适应更多的应用环境，还可以将掺杂剂与LiOH以及LiX等进行混合，并放入球磨罐中进行球磨处理，以便获得能够适应更多环境的反钙钛矿型固态电解质。根据本申请的实施例，该掺杂剂可以包括Na、Mg、Al元素的至少之一。例如，可以将含有Na+或者Mg 2+或者Al 3+的盐类物质与LiOH以及LiX等进行混合。
本领域技术人员能够理解的是，球磨处理过程中需要将球磨球同起始原料一起放入球磨罐中，随后将放有球磨球以及起始原料的球磨罐放入球磨机中进行球磨处理。关于球磨罐的具体类型不受特别限制，本领域技术人员可以根据具体情况进行设计。例如，根据本申请的实施例，该方法采用的球磨罐可以为氧化锆球磨罐，氧化锆球磨罐具有高硬度、高强度、高韧性以及极高的耐磨性、耐化学腐蚀性，球磨处理效果好。根据本申请的实施例，该方法采用的球磨球可以为氧化锆球，氧化锆球具有较好的强度以及硬度，可以配合氧化锆球磨罐达到良好的球磨处理效果，并且，利用氧化锆球可以不引入其他杂质，保证最终形成的反钙钛矿型固态电解质的纯度。
根据本申请的实施例，氧化锆球的直径可以为1.5-5mm。由此，可以保证氧化锆球对LiOH以及LiX等粉末具有较好的球磨效果。申请人发现，若氧化锆球的直径过大或过小，均会导致起始原料球磨不充分。根据本申请的具体实施例，氧化锆球的直径可以为4mm。
根据本申请的实施例，球磨罐的体积可以为40-60ml。由此，可以保证球磨处理的空间，进而获得较好的球磨效果。申请人发现，若球磨罐的体积过大或过小，均会导致起始原料球磨不充分。根据本申请的具体实施例，球磨罐的体积可以为55ml。
根据本申请的实施例，球磨处理的转速可以为300-550rpm。由此，可以使LiOH以及LiX等粉末发生反应，获得具有优良性能的反钙钛矿型固态电解质。根据本申请的具体实施例，球磨处理的转速可以为450rpm。
根据本申请的实施例，球磨处理的时间可以为4-6小时。由此，可以使LiOH以及LiX等粉末有充足的时间完成反应，保证最终获得的反钙钛矿型固态电解质具有良好的性能。申请人发现，球磨处理的时间过短，会导致起始原料反应不充分。而球磨处理的时间过长，并不会显著提高获得的反钙钛矿型材料的性能。根据本申请的具体实施例，球磨处理的时间可以为5.5小时。
在本申请的另一方面，本申请提出了一种反钙钛矿型固态电解质。根据本申请的实施例，该反钙钛矿型固态电解质是由前面描述的方法形成的，由此，该反钙钛矿型固态电解质具有优良的性能，且成本较低。
利用差示扫描量热法(DSC分析法)对根据本申请示例制备的反钙钛矿型固态电解质进行分析，参考图1，由球磨处理方法合成的反钙钛矿型固态电解质的玻璃化转变温度低于150℃，该反钙钛矿型固态电解质的熔点在270℃左右。为了获得该反钙钛矿型固态电解质的准确的玻璃化转变温度，将上述温度区间的DSC图谱进行放大，具体的，参考图2，该反钙钛矿型固态电解质具有两个玻璃化转变温度，第一个玻璃化转变温度在80℃左右，第二个玻璃化转变温度在115℃左右。由此，该反钙钛矿型固态电解质具有较低的玻璃化转变温度，从而可以使由该反钙钛矿型固态电解质构成的电池具有优良的使用性能。
根据本申请的实施例，利用核磁共振方法对由球磨处理方法合成的反钙钛矿型固态电解质以及利用固态合成方法合成的反钙钛矿型固态电解质进行分析，获得核磁共振氢谱(HNMR)，参考图3，由球磨处理方法合成的反钙钛矿型固态电解质不含有自由的H +，而由固态合成方法合成的反钙钛矿型固态电解质含有自由的H +。由此，由球磨处理方法合成的反钙钛矿型固态电解质具有优良的性能，可以省去后处理过程，例如，可以省去后续去除具有负面影响的自由的H +的处理步骤。
根据本申请的实施例，利用X射线衍射(XRD)对由球磨处理形成的反钙钛矿型固态电解质，分别在室温以及300℃的温度下进行测试，测试环境为氮气环境，参考图4，在室 温下，该反钙钛矿型固态电解质具有少量的氢氧化物，在300℃下，该反钙钛矿型固态电解质基本为非晶状态。根据本申请的实施例，该反钙钛矿型固态电解质的熔点在270℃左右，因此，将该反钙钛矿型固态电解质加热到300℃时，该反钙钛矿型固态电解质处于熔融状态，呈现非晶结构。根据本申请的实施例，由球磨处理形成的反钙钛矿型固态电解质具有较低的玻璃化转变温度，由此，在温度较低时(例如，低于玻璃化转变温度)，该反钙钛矿型固态电解质具有晶态结构，在温度较高时(例如，高于玻璃化转变温度)，该反钙钛矿型固态电解质具有非晶结构。上述XRD测试数据表明，利用该方法制备的反钙钛矿型固态电解质材料，具有与固态合成法制备的反钙钛矿型固态电解质相类似的特征。也即是说，该方法可以利用简单的球磨处理，获得性能良好的反钙钛矿型固态电解质材料。
在本申请的另一方面，本申请提出了一种电池。根据本申请的实施例，该电池包括前面描述的反钙钛矿型固态电解质。该电池还可以包括正极和负极，以及设置在正极和负极之间的固态电解质，固态电解质中包含上述反钙钛矿型材料。正极上具有正极活性材料，正极和负极之间形成电回路之后，可向外部设备供电。由此，该电池具有前面描述的反钙钛矿型固态电解质的全部特征以及优点，在此不再赘述。总的来说，该电池具有优良的使用性能，且成本较低。
在本申请的另一方面，本申请提出了一种车辆。根据本申请的实施例，该车辆包括前面描述的电池，由此，该车辆具有前面描述的电池的全部特征以及优点，在此不再赘述。该车辆具有车体、电子系统等结构，该电池可设置于车身中的固定位置处，例如可位于车体底部，且与电子系统相连，以便利用该电池，为车辆提供动力。总的来说，该车辆具有较低的成本以及较长的使用寿命。
下面通过具体的实施例对本申请的方案进行说明，需要说明的是，下面的实施例仅用于说明本申请，而不应视为限定本申请的范围。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。
实施例1
将3.372gLiOH、20925gLiCl、0.109gBa(OH) 2·8H 2O以及5ml水进行混合作为起始原料，并将上述起始原料与10g直径为3mm的氧化锆球一起放入50ml的氧化锆球磨罐中。随后将放有起始原料以及氧化锆球的氧化锆球磨罐放入Pulverisette 7型球磨机中，调整球磨机的转速为400rpm，球磨处理5h，最终获得反钙钛矿型固态电解质。
电化学性能检测
将实施例1获得的反钙钛矿型固态电解质制成1mm后的固体片，制成Li/Li 3OCl/Li的三明治结构，并进行电化学阻抗谱(EIS)以及电压稳定性测试，通过电化学阻抗测试，该电池具有高的导电率，通过电化学阻抗谱得出该电池的导电率不低于9ms/cm 2，以及通过 电压稳定性测试，该电池具有稳定的电化学窗口，参考图5。由此可知，利用该方法制备的反钙钛矿材料具有优良的性能，适于应用在锂离子电池中，做为固态电解质使用。
在本申请的描述中，术语“上”、“下”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请而不是要求本申请必须以特定的方位构造和操作，因此不能理解为对本申请的限制。
在本说明书的描述中，参考术语“一个实施例”、“另一个实施例”等的描述意指结合该实施例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。另外，需要说明的是，本说明书中，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。
尽管上面已经示出和描述了本申请的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本申请的限制，本领域的普通技术人员在本申请的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (16)

  1. 一种合成反钙钛矿型固态电解质的方法，所述反钙钛矿型固态电解质包括Li 3OX，所述X为卤素元素，所述方法包括：
    将LiOH以及LiX放入球磨罐中进行球磨处理，以便获得所述反钙钛矿型固态电解质。
  2. 根据权利要求1所述的方法，所述X为Cl、Br或I。
  3. 根据权利要求2所述的方法，所述X为Cl。
  4. 根据权利要求1-3任一项所述的方法，进一步包括：
    将掺杂剂与LiOH以及LiX混合，并放入所述球磨罐中进行球磨处理，所述掺杂剂包括Na、Mg、Al元素的至少之一。
  5. 根据权利要求1-4任一项所述的方法，进一步包括：
    将球磨球、Ba(OH) 2·8H 2O以及水放入所述球磨罐中进行球磨处理。
  6. 根据权利要求1-5任一项所述的方法，所述球磨处理采用的球磨罐为氧化锆球磨罐，球磨球为氧化锆球。
  7. 根据权利要求1-6任一项所述的方法，包括：将LiOH、LiX、Ba(OH) 2·8H 2O以及水混合并进行球磨处理，
    所述LiOH、LiX、Ba(OH) 2·8H 2O以及水的质量比为30:30:1:50。
  8. 根据权利要求1-7任一项所述的方法，所述球磨处理采用的氧化锆球的直径为1.5-5mm。
  9. 根据权利要求1-8任一项所述的方法，所述球磨处理采用的球磨罐的体积为40-60ml。
  10. 根据权利要求1-9任一项所述的方法，所述球磨处理的转速为300-550rpm。
  11. 根据权利要求1-10任一项所述的方法，所述球磨处理的时间为4-6小时。
  12. 一种反钙钛矿型固态电解质，所述反钙钛矿型固态电解质是由权利要求1-11任一项所述的方法形成的。
  13. 根据权利要求12所述的反钙钛矿型固态电解质，所述反钙钛矿型固态电解质中无自由H +存在。
  14. 根据权利要求12或13所述的反钙钛矿型固态电解质，反钙钛矿型固态电解质的玻璃化转变温度低于150℃。
  15. 一种电池，其特征在于，包括权利要求12-14任一项所述的反钙钛矿型固态电解质。
  16. 一种车辆，其特征在于，包括权利要求15所述的电池。
PCT/CN2018/125423 2017-12-29 2018-12-29 反钙钛矿型固态电解质及合成方法、电池、车辆 Ceased WO2019129267A1 (zh)

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