WO2019129262A1 - 处理反钙钛矿型固态电解质的方法、固态电解质、电池以及车辆 - Google Patents

处理反钙钛矿型固态电解质的方法、固态电解质、电池以及车辆 Download PDF

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WO2019129262A1
WO2019129262A1 PCT/CN2018/125385 CN2018125385W WO2019129262A1 WO 2019129262 A1 WO2019129262 A1 WO 2019129262A1 CN 2018125385 W CN2018125385 W CN 2018125385W WO 2019129262 A1 WO2019129262 A1 WO 2019129262A1
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ball
solid electrolyte
perovskite
powder
treatment
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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
    • H01M10/056—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
    • C01P2002/70—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
    • 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 energy and automobile manufacturing, and in particular, to a method of treating an anti-perovskite-type solid electrolyte, a solid electrolyte, a battery, and a vehicle.
  • Solid lithium ion conductors are mostly composed of an oxide-based compound, a sulfur-based compound, and a polymer.
  • the oxide-based solid lithium electrolyte has not been widely used due to defects such as low ion conductivity, poor stability of metallic lithium, and high glass transition temperature.
  • a sulfur-based solid electrolyte can provide high electrical conductivity, the voltage stabilization window is narrow and unstable on both lithium metal and high-voltage cathodes, requiring an expensive coating to function.
  • the polymer solid electrolyte is relatively soft and has been shown to have high stability to lithium metal. However, this type of solid electrolyte has low ion conductivity and low lithium ion mobility.
  • LiRAP anti-perovskite-type solid electrolyte
  • the above-mentioned fully dry state of the lithium ion battery needs to be processed at about 230-250 degrees Celsius to obtain, and usually the glass transition temperature of the LiRAP material is between 100 and 130 degrees Celsius. Therefore, a lithium ion battery using a LiRAP material cannot be assembled and used in a more preferable fully dried state. In other words, the LiRAP material is used in the presence of free H ions. This results in an unsatisfactory battery performance. Moreover, once the LiRAP material is dried at high temperature (230-250 ° C), its glass transition temperature will increase, that is, the LiRAP material after high temperature drying will lose its advantage of lower glass transition temperature.
  • both the LiRAP material can be dried and the lower glass transition temperature of the LiRAP material can be maintained, and the performance of the lithium ion battery fabricated using the material can be greatly improved.
  • the present application aims to solve at least one of the technical problems in the related art to some extent. To this end, it is an object of the present application to provide a method of obtaining a treated LiRAP material that does not contain free hydrogen ions and that has a low glass transition temperature.
  • the present application provides a method of treating an inverse perovskite-type solid electrolyte.
  • the anti-perovskite type solid electrolyte comprising Li 3 OX, X is a halogen element, the method comprising: Li 3 OX powder by drying; and after drying the treated powder was Li 3 OX milling process .
  • the LiRAP material treated by this method does not contain free hydrogen ions and the glass transition temperature remains low.
  • the drying treatment has a temperature of 200 to 250 degrees Celsius. Thereby, the Li 3 OX powder can be sufficiently dried.
  • the ball milling process comprises: mixing a ball mill ball with the Li 3 OX powder, and placing the mixture into a ball mill tank to perform the ball milling process, the ball milling process rotating at 300-550 rpm,
  • the ball milling treatment time is 4-6 h.
  • the ball-treated LiRAP material can restore a lower glass transition temperature. At this time, the material is dry and does not contain free hydrogen ions that are detrimental to battery performance.
  • the ball mill ball is a zirconia ball mill ball
  • the zirconia ball mill ball and the Li 3 OX powder have a mass ratio of 3:1 to 1:1.
  • the ball grinding ball and the Li 3 OX powder can be sufficiently mixed during the ball milling process.
  • the zirconia ball-milling ball has a diameter of 1.5 to 5 mm. Thereby, the efficiency and effect of the ball milling process can be improved.
  • the volume of the ball mill tank is 40-60 ml. Therefore, the efficiency and effect of the ball milling process can be improved.
  • the present application proposes a method of treating an inverse perovskite solid electrolyte.
  • the anti-perovskite solid electrolyte comprises Li 3 OX
  • the X is a halogen element
  • the method comprises: drying the Li 3 OX powder at 230 to 280 degrees Celsius, The drying treatment time is 4 to 6 hours; and the dried and treated Li 3 OX powder is subjected to a ball milling treatment, the ball milling treatment comprising: a zirconia ball mill ball having a diameter of 3 mm in a mass ratio of 2:1 and
  • the Li 3 OX powder was mixed and placed in a 50 ml zirconia ball mill jar and ball milled at 350 to 500 rpm for 5 hours.
  • the LiRAP material treated by this method does not contain free hydrogen ions and the glass transition temperature remains low.
  • the present application provides an anti-perovskite-type solid electrolyte that is treated by the methods described above.
  • the LiRAP material treated by this method does not contain free hydrogen ions and the glass transition temperature remains low.
  • the present application provides an anti-perovskite solid electrolyte.
  • the anti-perovskite-type solid electrolyte is formed by sequentially performing a drying treatment and a ball milling treatment, wherein the anti-perovskite-type solid electrolyte includes Li 3 OX, the X is a halogen element, and the anti-perovskite There is no free H + present in the solid electrolyte, and the glass transition temperature is lower than 150 ° C.
  • the anti-perovskite type solid electrolyte can improve the performance of a lithium ion battery using the electrolyte.
  • the present application proposes a battery.
  • the battery includes the anti-perovskite type solid electrolyte described above. Thereby, the performance of the lithium ion battery can be improved.
  • the present application proposes a vehicle.
  • the vehicle includes the battery described above.
  • the vehicle has all of the features and advantages of the lithium ion battery described above, and will not be described again.
  • FIG. 1 shows a schematic flow diagram of a method of treating an inverse perovskite-type solid electrolyte according to an embodiment of the present application
  • Figure 2 shows the results of nuclear magnetic resonance spectroscopy test
  • Figure 3 shows the results of differential scanning calorimetry analysis of the dried Li 3 OCl
  • Figure 6 shows the XRD test results of Li 3 OCl without ball milling
  • Figure 7 shows the XRD test results of the ball milled Li 3 OCl
  • Fig. 8 shows the results of electrical property test results of the solid electrolyte according to Example 1 of the present application.
  • the present application provides a method of treating an inverse perovskite-type solid electrolyte. According to an embodiment of the present application, referring to FIG. 1, the method includes:
  • the Li 3 OX powder is first subjected to a drying treatment.
  • the free hydrogen ions contained in the Li 3 OX powder can be removed in this step, so that the finally obtained anti-perovskite-type solid electrolyte (in Li 3 OX) is free from free H + . Therefore, it is possible to ensure that the lithium ion battery which is subsequently prepared by using the solid electrolyte can be operated in a fully dry state, thereby ensuring that the overall performance of the battery is not affected.
  • the glass transition temperature of Li 3 OX will be improved after drying, but this step can better remove free hydrogen ions, and the glass transition temperature can be after subsequent ball milling treatment. Reduce to a lower range.
  • the specific chemical composition of the anti-perovskite type solid electrolyte is not particularly limited, and for example, Li 3 OX may be included, wherein X is a halogen element, and may be, for example, Cl, Br or I.
  • the anti-perovskite solid electrolyte may be Li 3 OCl.
  • the specific method for producing Li 3 OCl is not particularly limited, and those skilled in the art can select a familiar method to prepare Li 3 OCl.
  • Li 3 OCl can be synthesized by means including, but not limited to, hydrothermal methods.
  • the chemical reaction formula for the synthesis of Li 3 OCl is as follows:
  • the temperature and time of the drying treatment in this step are not particularly limited as long as the free hydrogen ions in the Li 3 OX powder can be removed.
  • the Li 3 OX powder can be dried in an environment of 200 to 250 degrees Celsius.
  • the drying time can be from 3 to 6 hours.
  • the inventors have found through intensive studies that for Li 3 OX powder, especially for Li 3 OCl, the drying temperature for removing free hydrogen ions is around 220 degrees Celsius.
  • the drying treatment can be carried out at 230 to 250 degrees Celsius, and the drying time can be 5 hours. Thereby, free hydrogen ions in the Li 3 OX powder can be effectively removed to obtain a dried Li 3 OX powder.
  • the step includes subjecting the dried Li 3 OX powder to a ball milling treatment.
  • the inventors have unexpectedly found that by subjecting the dried Li 3 OX powder to ball milling under appropriate conditions, the glass transition temperature of the dried Li 3 OX powder can be further reduced to a lower range.
  • the LiRAP material treated by this method can contain neither free hydrogen ions nor a low glass transition temperature.
  • a ball mill ball may be mixed with the Li 3 OX powder, and the mixture may be placed in a ball mill tank for ball milling treatment.
  • the above ball milling treatment can be carried out using a zirconia ball mill ball and a zirconia ball mill pot.
  • the mass ratio of the zirconia ball mill ball and the Li 3 OX powder may be from 3:1 to 1:1.
  • the mass of the zirconia ball mill ball can be made twice that of the Li 3 OX powder.
  • the zirconia ball mill ball may have a diameter of 1.5-5 mm.
  • the efficiency and effect of the ball milling process can be improved.
  • a zirconia ball mill ball having a diameter of 3 mm can be used.
  • the volume of the ball mill can be selected according to the amount of the ball mill ball and the Li 3 OX powder, so that a proper space is reserved, and the ball mill ball and the powder can be sufficiently moved and ground.
  • a ball mill can be used with a volume of 40-60 ml. Thereby, the efficiency and effect of the ball milling process can be improved.
  • the rotational speed of the ball milling process may be 300-550 rpm, and the time of the ball milling process may be 4-6 h.
  • ball milling can be carried out for 5 hours at 350, 400, 450 or at 500 rpm.
  • the inventors have surprisingly found that the ball-treated LiRAP material can restore a lower glass transition temperature. At this point the material has been dried and does not contain free hydrogen ions that are detrimental to battery performance. This shift may be due to the recombination of the phases in the LiRAP material during the ball milling process and the change in the ratio between the different phases. Thereby, a dry LiRAP material solid electrolyte having a glass transition temperature of about 100 to 130 degrees Celsius can be easily obtained.
  • the present application proposes a method of treating an inverse perovskite solid electrolyte.
  • the anti-perovskite-type solid electrolyte includes Li 3 OX, and X is a halogen element.
  • the method comprises: drying the Li 3 OX powder at 230 to 280 degrees Celsius, and the drying treatment time is 4 to 6 hours. Subsequently, the dried Li 3 OX powder was subjected to a ball milling treatment.
  • the ball milling treatment may include mixing a zirconia ball mill ball having a diameter of 3 mm with a Li 3 OX powder at a mass ratio of 2:1 and placing it in a 50 ml zirconia ball mill tank. Ball milling was carried out for 5 hours at a rotational speed of 350 to 500 rpm.
  • the LiRAP material treated by this method does not contain free hydrogen ions and the glass transition temperature remains low.
  • the present application provides an anti-perovskite solid electrolyte.
  • the anti-perovskite solid electrolyte is treated by the method described above.
  • the anti-perovskite-type solid electrolyte has all of the features and advantages of the solid electrolyte obtained by the treatment method described above, and will not be described herein.
  • the LiRAP material treated by this method does not contain free hydrogen ions and the glass transition temperature remains low.
  • the present application provides an anti-perovskite solid electrolyte.
  • the anti-perovskite solid electrolyte is formed by sequentially performing a drying treatment and a ball milling treatment, wherein the anti-perovskite solid electrolyte includes Li 3 OX, X is a halogen element, and there is no freedom in the anti-perovskite solid electrolyte. H + is present and the glass transition temperature is below 150 °C.
  • the anti-perovskite type solid electrolyte can improve the performance of a lithium ion battery using the electrolyte.
  • the present application proposes a battery.
  • the battery includes the anti-perovskite type solid electrolyte described above.
  • the performance of the lithium ion battery can be improved.
  • the electrical properties of the battery can be closer to what the theoretical LiRAP material can achieve.
  • the present application proposes a vehicle.
  • the vehicle includes the battery described above.
  • the vehicle has all of the features and advantages of the lithium ion battery described above, and will not be described again.
  • the vehicle can be an electric vehicle that can power the vehicle.
  • the electrical properties of the battery can be closer to what the theoretical LiRAP material can achieve. Therefore, the vehicle also has the advantage of being more endurance.
  • the nuclear perovskiro-type solid electrolyte treated in Example 1 was subjected to nuclear magnetic resonance spectroscopy (HNMR).
  • HNMR nuclear magnetic resonance spectroscopy
  • the dried perovskite-type solid product did not contain free H + .
  • LiOH after drying treatment also does not contain free H +
  • other control samples anti-perovskite solid electrolyte before drying, water and undried LiOH
  • free H + ie free H +
  • DSC analysis Differential scanning calorimetry
  • Li 3 OCl did not show a glass transition-related peak between 100 and 130 degrees Celsius, and the melting point of low-temperature hydroxide (about 220 degrees Celsius) did not appear.
  • the DSC spectrum was only about 275 degrees Celsius, and the anti-retention was retained.
  • the melting point peak of the perovskite phase From this it can be proved that the heat treatment can effectively remove free hydrogen ions and obtain Li 3 OCl which does not contain free H + .
  • Li 3 OCl in Example 1 was subjected to differential scanning calorimetry (DSC analysis) analysis.
  • DSC analysis differential scanning calorimetry
  • Fig. 4 and Fig. 5 partially enlarged view of Fig. 4
  • Li 3 OC reappears the glass transition peak at about 120 degrees Celsius. It can be seen that the anti-perovskite solid electrolyte restores a lower glass transition temperature.
  • the non-ball-milled and ball-milled Li 3 OCl was tested by X-ray diffraction (XRD) (at room temperature and at a temperature of 300 ° C), and the test environment was a nitrogen atmosphere.
  • XRD X-ray diffraction
  • the non-ball milled Li 3 OCl exhibits material properties similar to glass at room temperature and at 300 ° C: the characteristic peak is mainly composed of an amorphous phase accompanied by a high temperature hydroxide phase. peak.
  • Example 1 The Li 3 OCl obtained in Example 1 was subjected to a tableting treatment (1 mm thick), and a Li/Li 3 OCl/Li battery was composed for testing. Referring to Figure 8, the battery exhibited good stability, indicating that the solid electrolyte prepared in Example 1 was suitable for use in the preparation of a lithium ion battery.

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Abstract

提出了处理反钙钛矿型固态电解质的方法、固态电解质、电池以及车辆。该方法包括：将Li3OX粉末进行干燥处理；以及对经过所述干燥处理的Li3OX粉末进行球磨处理。

Description

处理反钙钛矿型固态电解质的方法、固态电解质、电池以及车辆 技术领域
本申请涉及能源以及汽车制造领域，具体地，本申请涉及处理反钙钛矿型固态电解质的方法、固态电解质、电池以及车辆。
背景技术
对于锂离子电池而言，特别是全固态锂离子电池，固体锂离子导体，或固态电解质，是影响电池性能的重要因素。固体锂离子导体多由氧化物基化合物、硫基化合物和聚合物构成。其中，氧化物基固体锂电解质由于离子导电性低、金属锂稳定性差以及玻璃化转变温度较高等缺陷，未能够获得广泛的应用。硫基固体电解质虽然能够提供高电导率，但电压稳定窗口较窄，且在锂金属和高压阴极上都不稳定，需要昂贵的涂层才能发挥作用。聚合物固体电解质较软，已证明对锂金属具有很高的稳定性，然而该类型的固体电解质离子传导率低，锂离子迁移率低。
因此，目前处理固态电解质的方法及固态电解质，仍有待改进。
申请内容
本申请是基于发明人对以下事实和问题的发现和认识作出的：
近年来反钙钛矿型固态电解质(LiRAP)，由于锂金属稳定性好和玻璃化转变温度低，可形成非晶玻璃无晶界等优点，吸引了研究人员的广泛关注。虽然LiRAP材料的理论性能较为优越，然而利用LiRAP材料制备的锂离子电池的性能，却难以达到其理论上可以获得的优越性能。发明人经过深入研究发现，这主要是由于在锂离子电池中，全干燥(电池内部不含水)的状态下才能够体现该电池的最好性能。锂离子电池的上述全干燥状态需要在230-250摄氏度左右进行处理才能够获得，而通常LiRAP材料的玻璃化温度，在100-130摄氏度之间。因此，利用LiRAP材料的锂离子电池，实际无法在较为优选的全干燥状态下进行组装使用。换句话说，LiRAP材料是在含有游离H离子的情况下被使用的。由此造成了电池性能的不理想。并且，LiRAP材料一旦经高温(230-250摄氏度)干燥后，其玻璃化温度将升高，即：高温干燥后的LiRAP材料将丧失其玻璃化转变温度较低的优势。因此，如能够提供一种处理LiRAP固态电解质的方法，使得既可以令LiRAP材料干燥，又可以保持LiRAP材料较低的玻璃化温度，则能够大幅提高利用该材料制备的锂离子电池的性能。
本申请旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本申请的一个目的在于提出一种可以获得不含自由氢离子且玻璃化转变温度保持较低的处理LiRAP材料的方法。
在本申请的一个方面，本申请提出一种处理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Li 3OX粉末进行干燥处理；以及对经过所述干燥处理的Li 3OX粉末进行球磨处理。经过该方法处理的LiRAP材料中，不含自由氢离子且玻璃化转变温度保持较低。
根据本申请的实施例，所述干燥处理的温度为200～250摄氏度。由此，可以较为充分的干燥Li 3OX粉末。
根据本申请的实施例，所述球磨处理包括：将球磨球与所述Li 3OX粉末混合，并将混合物放入球磨罐中进行所述球磨处理，所述球磨处理的转速为300-550rpm，所述球磨处理的时间为4-6h。经过球磨处理后的LiRAP材料可以恢复较低的玻璃化转变温度。且此时材料已干燥，不含有不利于电池性能的自由氢离子。
根据本申请的实施例，所述球磨球为氧化锆球磨球，氧化锆球磨球以及所述Li 3OX粉末的质量比为3:1～1:1。由此，可较为充分的令球磨球以及Li 3OX粉末在球磨过程中进行混合。
根据本申请的实施例，所述氧化锆球磨球的直径为1.5-5mm。由此，可提高球磨处理的效率以及效果。
根据本申请的实施例，所述球磨罐的体积为40-60ml。由此，可提高球磨处理的效率以及效果。
在本申请的另一方面，本申请提出了一种处理反钙钛矿型固态电解质的方法。根据本申请的实施例，该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Li 3OX粉末在230～280摄氏度下进行干燥处理，所述干燥处理的时间为4～6小时；以及对经过所述干燥处理的Li 3OX粉末进行球磨处理，所述球磨处理包括：将直径为3mm的氧化锆球磨球按照质量比为2:1与所述Li 3OX粉末进行混合并置于50ml的氧化锆球磨罐中，并在350～500rpm的转速下，球磨5小时。经过该方法处理的LiRAP材料中，不含自由氢离子且玻璃化转变温度保持较低。
在本申请的又一方面，本申请提出了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经前面所述的方法处理的。经过该方法处理的LiRAP材料中，不含自由氢离子且玻璃化转变温度保持较低。
在本申请的又一方面，本申请提出了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依次经过干燥处理以及球磨处理而形成的，其中，所述反钙钛矿型固态电解质包括Li 3OX,所述X为卤素元素，所述反钙钛矿型固态电解质中无自由H +存在，玻璃化转变温度低于150℃。该反钙钛矿型固态电解质能够提高利用该电解质的锂离子电池的性能。
在本申请的又一方面，本申请提出了一种电池。该电池包括前面所述的反钙钛矿型固态电解质。由此，可以提高该锂离子电池的性能。
在本申请的又一方面，本申请提出了一种车辆。该车辆包括前面所述的电池。由此，该车辆具有前面描述的锂离子电池的全部特征以及优点，在此不再赘述。
附图说明
图1显示了根据本申请一个实施例的处理反钙钛矿型固态电解质的方法的流程示意图；
图2显示了核磁共振氢谱测试结果；
图3显示了经过干燥处理的Li 3OCl的差示扫描量热法分析结果；
图4以及图5显示了经过球磨处理的Li 3OCl的差示扫描量热法分析结果；
图6显示了未经球磨处理的Li 3OCl的XRD测试结果；
图7显示了经过球磨处理的Li 3OCl的XRD测试结果；以及
图8显示了根据本申请实施例1的固态电解质的电学性能测试结结果。
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。下面通过参考附图描述的实施例是示例性的，旨在用于解释本申请，而不能理解为对本申请的限制。
在本申请的一个方面，本申请提出一种处理反钙钛矿型固态电解质的方法。根据本申请的实施例，参考图1，该方法包括：
S100：干燥处理
根据本申请的实施例，在该步骤中，首先对Li 3OX粉末进行干燥处理。由此，可以在该步骤中去除Li 3OX粉末中含有的自由氢离子，使最终获得的反钙钛矿型固态电解质中(Li 3OX中)无自由H +存在。从而可以保证后续利用该固态电解质制备的锂离子电池，能够在全干燥状态下进行工作，从而保证电池的整体性能不受影响。
本领域技术人员能够理解的是，经过干燥处理后，Li 3OX的玻璃化温度将会提升，但该步骤可以较好的去除自由氢离子，且玻璃化转变温度可在后续的球磨处理之后，降低至较低的范围。
根据本申请的实施例，反钙钛矿型固态电解质的具体化学组成不受特别限制，例如，可以包括Li 3OX，其中X为卤素元素，例如可以为Cl、Br或是I。具体的，反钙钛矿型固态电解质可以为Li 3OCl。制备获得Li 3OCl的具体方法不受特别限制，本领域技术人员可以选择熟悉的方法，制备Li 3OCl。例如，可以采用包括但不限于水热法等方式，合成Li 3OCl。合成Li 3OCl的化学反应式如下所示：
Figure PCTCN2018125385-appb-000001
根据本申请的实施例，该步骤中干燥处理的温度、时间不受特别限制，只要可以去除Li 3OX粉末中的自由氢离子即可。例如，可将Li 3OX粉末置于200～250摄氏度的环境中进 行干燥。干燥的时间可以为3～6小时。发明人经过深入研究发现，对于Li 3OX粉末，特别是对于Li 3OCl而言，去除自由氢离子的干燥温度在220摄氏度左右。由此，可以在230～250摄氏度下，进行干燥处理，干燥时间可以为5小时。由此，可以有效去除Li 3OX粉末中的自由氢离子，获得干燥的Li 3OX粉末。
S200：球磨处理
根据本申请的实施例，该步骤包括：对经过干燥处理的Li 3OX粉末进行球磨处理。发明人意外地发现，将干燥后的Li 3OX粉末，在适当条件下进行球磨处理，可以将经过干燥后的Li 3OX粉末的玻璃化温度重新降至较低的范围内。由此，经过该方法处理的LiRAP材料中，可以既不含自由氢离子，同时保持玻璃化转变温度较低。
根据本申请的实施例，球磨处理的具体条件不受特别限制。例如，可以将球磨球与所述Li 3OX粉末混合，并将混合物放入球磨罐中进行球磨处理。其中，可以采用氧化锆球磨球以及氧化锆球磨罐进行上述球磨处理。由此，可以保证球磨处理的质量，同时保证不会在球磨过程中，在Li 3OX粉末中引入新的杂质。氧化锆球磨球以及Li 3OX粉末的质量比可以为3:1～1:1。例如，可以令氧化锆球磨球的质量，为Li 3OX粉末质量的2倍。由此，可较为充分的令球磨球以及Li 3OX粉末在球磨过程中进行混合。根据本申请的实施例，氧化锆球磨球的直径可以为1.5-5mm。由此，可提高球磨处理的效率以及效果。例如，根据本申请的具体实施例，可以采用直径为3mm的氧化锆球磨球。球磨罐的体积可以根据球磨球以及Li 3OX粉末的量进行选择，以预留有适当空间，可令球磨球和粉末之间能够充分的运动研磨即可。在此基础上，可以采用体积为40-60ml的球磨罐。由此，可提高球磨处理的效率以及效果。
根据本申请的实施例，球磨处理的转速可以为300-550rpm，球磨处理的时间可以为4-6h。根据本申请的具体实施例，可以在350、400、450或在500rpm的转速下，球磨5小时。发明人惊奇的发现，经过球磨处理后的LiRAP材料可以恢复较低的玻璃化转变温度。且此时材料已被干燥，不含有不利于电池性能的自由氢离子。这一转变可能是由于球磨处理过程中，LiRAP材料中的各相发生了重组，不同相之间的比例发生了改变而导致的。由此，可以简便地获得干燥的、且玻璃化转变温度维持在100～130摄氏度左右的LiRAP材料固态电解质。
在本申请的另一方面，本申请提出了一种处理反钙钛矿型固态电解质的方法。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。该方法包括：将Li 3OX粉末在230～280摄氏度下进行干燥处理，干燥处理的时间为4～6小时。随后，对经过干燥处理的Li 3OX粉末进行球磨处理。球磨处理可包括：将直径为3mm的氧化锆球磨球按照质 量比为2:1与Li 3OX粉末进行混合，并置于50ml的氧化锆球磨罐中。在350～500rpm的转速下，球磨5小时。经过该方法处理的LiRAP材料中，不含自由氢离子且玻璃化转变温度保持较低。
在本申请的又一方面，本申请提出了一种反钙钛矿型固态电解质。该反钙钛矿型固态电解质是经前面所述的方法处理的。由此，该反钙钛矿型固态电解质具有前面描述的处理方法获得的固态电解质所具有的全部特征以及优点，在此不再赘述。经过该方法处理的LiRAP材料中，不含自由氢离子且玻璃化转变温度保持较低。
在本申请的又一方面，本申请提出了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依次经过干燥处理以及球磨处理而形成的，其中，反钙钛矿型固态电解质包括Li 3OX,X为卤素元素，反钙钛矿型固态电解质中无自由H +存在，玻璃化转变温度低于150℃。该反钙钛矿型固态电解质能够提高利用该电解质的锂离子电池的性能。
在本申请的又一方面，本申请提出了一种电池。该电池包括前面所述的反钙钛矿型固态电解质。由此，可以提高该锂离子电池的性能。例如，该电池的电学性能，可以与理论上LiRAP材料可以达到的性能更加接近。
在本申请的又一方面，本申请提出了一种车辆。该车辆包括前面所述的电池。由此，该车辆具有前面描述的锂离子电池的全部特征以及优点，在此不再赘述。例如，该车辆可以为电动汽车，上述电池可为驱动该车辆提供动力。例如，该电池的电学性能，可以与理论上LiRAP材料可以达到的性能更加接近。因此，该车辆也具有续航能力更强等优点。
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10g的氧化锆球磨球(3mm)与5g的Li 3OCl粉末混合，在250摄氏度下加热5小时彻底干燥。随后置于50ml容积的氧化锆球磨罐中，采用Pulverisette7型球磨机进行球磨处理。转速为350rpm～500rpm，时间5小时。
性能检测
对实施例1处理后的反钙钛矿型固态电解质进行核磁共振氢谱测试(HNMR)，参考图2，干燥处理后的反钙钛矿型固态电解质(product dry)不含有自由的H +，干燥处理后的LiOH也不含有游离态H +，而其他对照样品(干燥处理之前的反钙钛矿型固态电解质、水以及未 干燥的LiOH)中，均含有自由的H +(即游离态H +)。对经过干燥处理，但未经过球磨处理的Li 3OCl进行差示扫描量热法(DSC分析法)分析，结果参见图3。干燥处理后的Li 3OCl未在100～130摄氏度之间出现玻璃化转变相关峰，低温氢氧化物的熔点(220摄氏度左右)也未出现，DSC谱图上仅在275摄氏度左右，保留了反钙钛矿相的熔点峰。在由此可以证明，加热处理可以有效去除自由氢离子，获得不含有自由的H +的Li 3OCl。
对实施例1中经过球磨处理的Li 3OCl进行差示扫描量热法(DSC分析法)分析。参考图4以及图5(图4局部放大图)，Li 3OC在120摄氏度左右，重新出现了玻璃化转变峰。由此可知，反钙钛矿型固态电解质恢复了较低的玻璃化转变温度。
根据本申请的实施例，利用X射线衍射(XRD)对未经过球磨处理，以及经过球磨处理的Li 3OCl进行测试(室温以及300℃的温度下)，测试环境为氮气环境。参考图6，未经球磨处理的Li 3OCl在室温下，以及在300℃下，均表现出类似于玻璃的材料特性：特征峰主要由非晶相构成，且伴有高温氢氧化物相的尖峰。对比经过球磨处理的Li 3OCl的XRD测试结果(参考图7)可知，该材料在球磨处理的过程中，经历了相重组的过程，且高温(300摄氏度)下测得的XRD结果主要表现为非晶相组成。
将实施例1获得的Li 3OCl进行压片处理(1mm厚)，并组成Li/Li 3OCl/Li电池进行测试。参考图8，该电池表现出良好的稳定性，表明实施例1所制备的固态电解质，适用于制备锂离子电池。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例或示例中。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。
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 (14)

  1. 一种处理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Li 3OX粉末进行干燥处理；以及
    对经过所述干燥处理的Li 3OX粉末进行球磨处理。
  2. 根据权利要求1所述的方法，所述干燥处理的温度为200～250摄氏度。
  3. 根据权利要求1或2所述的方法，所述球磨处理包括：
    将球磨球与所述Li 3OX粉末混合，并将混合物放入球磨罐中进行所述球磨处理，所述球磨处理的转速为300-550rpm，所述球磨处理的时间为4-6小时。
  4. 根据权利要求3所述的方法，所述球磨球为氧化锆球磨球，所述氧化锆球磨球以及所述Li 3OX粉末的质量比为3:1～1:1。
  5. 根据权利要求3或4所述的方法，氧化锆球磨球的直径为1.5-5mm。
  6. 根据权利要求3-5任一项所述的方法，所述球磨罐的体积为40-60ml。
  7. 根据权利要求1所述的方法，所述方法包括：
    将Li 3OX粉末在230～280摄氏度下进行干燥处理，所述干燥处理的时间为4～6小时；以及
    对经过所述干燥处理的Li 3OX粉末进行球磨处理，所述球磨处理包括：
    将直径为3mm的氧化锆球磨球按照质量比为2:1与所述Li 3OX粉末进行混合并置于50ml的氧化锆球磨罐中，并在350～500rpm的转速下，球磨5小时。
  8. 根据权利要求1-7任一项所述的方法，所述球磨处理后，所述Li 3OX粉末的玻璃化转变温度为100～130摄氏度。
  9. 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依次经过干燥处理以及球磨处理而形成的。
  10. 根据权利要求9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包括Li 3OX,所述X为卤素元素，所述反钙钛矿型固态电解质中无自由H +存在，玻璃化转变温度低于150℃。
  11. 根据权利要求10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，为所述Li 3OX的核磁共振氢谱中，无自由H +对应的特征峰。
  12. 根据权利要求9-11任一项所述的反钙钛矿型固态电解质，所述Li 3OX的XRD谱图，无高温氢氧化物相对应特征峰。
  13. 一种电池，其特征在于，包括权利要求9-12任一项所述的反钙钛矿型固态电解质。
  14. 一种车辆，其特征在于，包括权利要求13所述的电池。
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CN110635113B (zh) * 2019-08-16 2021-09-03 南方科技大学 锂负极或钠负极及锂负极或钠负极的制备方法和应用
CN113735145A (zh) * 2020-05-28 2021-12-03 中国科学院上海硅酸盐研究所 一种阴阳离子共掺杂的富钠相反钙钛矿型固态电解质材料及其制备方法和全固态钠电池
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