WO2023130671A1 - 一种复合固态电解质材料及其制备方法和应用 - Google Patents

一种复合固态电解质材料及其制备方法和应用 Download PDF

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WO2023130671A1
WO2023130671A1 PCT/CN2022/098509 CN2022098509W WO2023130671A1 WO 2023130671 A1 WO2023130671 A1 WO 2023130671A1 CN 2022098509 W CN2022098509 W CN 2022098509W WO 2023130671 A1 WO2023130671 A1 WO 2023130671A1
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solid electrolyte
electrolyte material
composite solid
ball milling
lithium
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French (fr)
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张耀
吴子强
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东南大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • 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

Definitions

  • the invention belongs to a solid electrolyte material, in particular to a (xLiBH 4 -yLiI)-zBN composite solid electrolyte material with an amorphous and heterojunction interface and a preparation method and application thereof.
  • Lithium-ion secondary batteries have been widely used for their high energy and power density, long life, and environmental protection, especially in electric vehicles and portable devices.
  • Conventional Li-ion batteries tend to use organic liquid electrolytes with high ionic conductivity, but cause reversible capacity fading and serious safety concerns due to their volatility, flammability, and easy formation of Li dendrites. These issues have long hindered the development of lithium batteries.
  • the use of solid electrolytes can improve the safety and performance of lithium batteries, and replacing the electrolyte and diaphragm in traditional lithium batteries can achieve system simplification and efficient use of materials.
  • Oxide- and sulfide-based solid-state electrolytes have similar or slightly lower ionic conductivity than liquid electrolytes, but the stability and electrode compatibility cannot meet the requirements of all-solid-state lithium batteries.
  • LiBH 4 is a kind of coordination metal hydride. As a solid electrolyte, it has a wide electrochemical window and is compatible with most electrodes. The main disadvantage is its low room temperature conductivity ( ⁇ 10 -7 S cm -1 ). Therefore, how to reduce the phase transition temperature of the LiBH 4 system, so that it can stabilize the high-temperature phase at room temperature, so as to meet the requirements of solid-state electrolytes for all-solid-state lithium-ion batteries is an urgent research direction.
  • the purpose of the present invention is to provide a composite solid electrolyte material which is composited by borohydride and hexagonal boron nitride to form an amorphous and heterojunction mixed interface;
  • the second purpose of the present invention is to provide the above composite solid electrolyte material Preparation method;
  • the third object of the present invention is to provide the application of the above-mentioned composite solid electrolyte material in the preparation of battery electrolyte.
  • a composite solid electrolyte material of the present invention the electrolyte material has an amorphous and heterojunction mixed interface;
  • the chemical composition is (xLiBH 4 -yLiI)-zBN, wherein x, y, z are molar ratios, and 1 ⁇ x ⁇ 5, 0 ⁇ y ⁇ 5, 1 ⁇ z ⁇ 5.
  • the low-temperature ionic conductivity of the electrolyte material is (0.61-4.21) ⁇ 10 -4 Scm -1 ; wherein, the low-temperature range is 30-50 degrees Celsius.
  • the preparation method of the above-mentioned composite solid electrolyte material comprises the following steps:
  • Hexagonal boron nitride is subjected to high-energy ball milling under the protection of an inert atmosphere to prepare hexagonal boron nitride containing an amorphous structure;
  • the ball-to-material ratio of the high-energy ball mill is (40-45):1, the rotation speed is 450-550 rpm, and the ball milling time is 5-20 hours.
  • the ball-to-material ratio of the high-energy ball mill is (40-45):1
  • the rotation speed is 500-550 rpm
  • the ball milling time is 2-5 hours.
  • the hydrogen pressure of the heat treatment is 2-10 MPa
  • the heat treatment temperature is 270-300 degrees Celsius
  • the heating rate is 2-10 degrees Celsius/minute
  • the holding time is 6-12 hours.
  • the ball-to-material ratio of the high-energy ball mill is (40-45):1, the rotation speed is 400-500 rpm, and the ball milling time is 5-10 hours.
  • the hydrogen pressure of the heat treatment is 2-10 MPa
  • the heat treatment temperature is 150-340 degrees Celsius
  • the heating rate is 2-10 degrees Celsius/minute
  • the holding time is 2-24 hours.
  • the above-mentioned composite solid electrolyte material can be used as a solid electrolyte for preparing lithium-ion batteries.
  • a composite interface including heterojunction and amorphous structure is constructed by borohydride and hexagonal boron nitride; hexagonal boron nitride produces some defects and is amorphous under ball milling treatment.
  • the hexagonal boron nitride causes the B-H bond distortion in the borohydride to lead to the amorphization of the borohydride, and the amorphous interface between the two amorphous phases forms a fast channel for lithium ion migration, which improves the ion conductivity at low temperature; at the same time , There is also an intercrystalline contact between borohydride and hexagonal boron nitride, forming a heterojunction structure that facilitates electron separation and improves the performance of solid-state batteries.
  • the ionic conductivity of the composite material prepared by the present invention is about 3 to 4 orders of magnitude higher than that of LiBH 4 at low temperatures, especially at 30-50 degrees Celsius, which can reach 10 -4 S cm -1 ; and has a wider electrochemical Stable window (-1-5V vs. Li + ), high lithium ion mobility (97%), almost negligible electronic conductivity (10 -10 -10 -9 S cm -1 ), is an excellent lithium ion conductor .
  • the compound prepared by the present invention can stably circulate lithium for more than 500 hours at a constant current, and has good compatibility and electrochemical stability with lithium electrodes; the critical current density is above 4.6mA cm -2 , showing extremely strong lithium Dendrite suppression ability.
  • the compound prepared in the present invention can be assembled into a TiS 2 -Li all-solid-state battery, and the capacity retention rate of the TiS 2 -Li all-solid-state battery can reach 93% after 10 cycles, and can be used as a solid-state electrolyte for an all-solid-state lithium-ion battery , with commercial application value.
  • Figure 3 is a comparison of X-ray diffraction patterns of pretreated BN, pure LiBH 4 , 3LiBH 4 -LiI and (3LiBH 4 -LiI)-2BN;
  • Fig. 6 is the Fourier transform infrared spectrogram of the material (3LiBH 4 -LiI)-2BN prepared by ball milling and heat treatment;
  • Figure 7 is a high-resolution transmission electron micrograph of the interface of the material LiBH 4 -2BN prepared by ball milling and heat treatment;
  • Figure 8 is a high-resolution transmission electron micrograph of the interface of the material (3LiBH 4 -LiI)-2BN prepared by ball milling and heat treatment;
  • Figure 11 is the cyclic voltammetry curve of the material LiBH 4 -2BN prepared by ball milling and heat treatment
  • Figure 12 is the cyclic voltammetry curve of the material (3LiBH 4 -LiI)-2BN prepared by ball milling and heat treatment;
  • Figure 13 is the ion mobility diagram of the material LiBH 4 -2BN prepared by ball milling and heat treatment
  • Figure 14 is the ion mobility diagram of the material (3LiBH 4 -LiI)-2BN prepared by ball milling and heat treatment;
  • Figure 15 is the electronic conductivity diagram of the material LiBH 4 -2BN prepared by ball milling and heat treatment
  • Figure 16 is the electronic conductivity diagram of the material (3LiBH 4 -LiI)-2BN prepared by ball milling and heat treatment;
  • Figure 17 is the galvanostatic versus lithium cycle diagram of the material LiBH 4 -2BN prepared by ball milling and heat treatment;
  • Figure 18 is the galvanostatic diagram of the lithium cycle of the material (3LiBH 4 -LiI)-2BN prepared by ball milling and heat treatment;
  • Fig. 19 is a diagram of increasing current versus lithium cycle of the material LiBH 4 -2BN prepared by ball milling and heat treatment;
  • Fig. 20 is a diagram of increasing current versus lithium cycle of the material (3LiBH 4 -LiI)-2BN prepared by ball milling and heat treatment;
  • Fig. 21 is a constant current charge and discharge curve and cycle diagram of a TiS2-Li battery assembled from materials LiBH 4 -2BN prepared by ball milling and heat treatment.
  • the total mass of the sample in the spherical tank is 0.5 g
  • the volume of the ball milling tank is 100 ml
  • the weight ratio of the balls to the sample is 40:1
  • the ball milling time is 5 hours
  • the revolution speed is set at 450 rpm.
  • Put the mixture obtained by ball milling into a Sievert type gas-solid reaction PCT device, and heat treat under a certain hydrogen pressure to obtain LiBN 4 -zBN composites, z 1, 2, 3; during the heat treatment, the hydrogen pressure is 4 MPa, and the heat treatment temperature It is 295 degrees Celsius, the heating rate is 10 degrees Celsius/minute, and the holding time is 24 hours.
  • the mixture of LiBH 4 and LiI was loaded into a Sievert type gas-solid reaction PCT device, and heat treated under a certain hydrogen pressure to obtain 3LiBH 4 -LiI solid solution.
  • the hydrogen pressure was 4 MPa
  • the heat treatment temperature was 275 degrees Celsius
  • the heating rate was 6 degrees Celsius/min
  • the holding time was 12 hours.
  • the total mass of the sample in the spherical tank is 0.5 g
  • the volume of the ball milling tank is 100 ml
  • the weight ratio of the balls to the sample is 40:1
  • the ball milling time is 10 hours
  • the revolution speed is set at 450 rpm.
  • the hydrogen pressure was 8 MPa
  • the heat treatment temperature was 150 degrees Celsius
  • the heating rate was 2 degrees Celsius/min
  • the holding time was 2 hours.
  • the target material of the X-ray source used is a Cu target, the tube voltage is 40kV, and the tube current is 40mA.
  • FTIR Fourier transform infrared spectroscopy
  • LiBH 4 -2BN composite particles of Example 1 and the (3LiBH 4 -LiI)-2BN composite particles of Example 2 and analyze their microscopic morphology and phase structure using a high-resolution transmission electron microscope , Mix a small amount of composite particles with alcohol, ultrasonically disperse for two minutes to make them evenly dispersed, and then absorb a small amount of the mixed liquid and drop it on the copper grid for testing.
  • the ionic conductivity performance test of the sample is obtained by the AC impedance test method on the electrochemical workstation.
  • the samples obtained in Example 1 and Example 2 were pressed into a disc with a diameter of 10 mm and a thickness of about 1 mm with a pressure of 10-20 MPa.
  • the sandwich structure lithium sheet/solid electrolyte sheet/lithium sheet
  • two lithium foils are placed on both sides of the sample disc as electrodes. Then press the lithium foil and the sample sheet tightly with a pressure of 1 to 10 tons/square centimeter. All preparations were performed under high purity argon (99.9999%).
  • the frequency range of the AC impedance test is from 1MHz to 1Hz.
  • the sample was heated at a rate of 2°C/min, and the impedance spectrum was collected every 5-10°C.
  • the temperature rises from room temperature to 120 degrees Celsius.
  • the ionic conductivity can be obtained by fitting the obtained AC impedance Nyquist spectrum and Zview, and the change curve of conductivity with temperature can be made.
  • the molar ratio is 1:2
  • the ionic conductivity of the composite can reach the order of 10 -4 S cm -1 at 40°C.
  • Due to the extremely poor ionic conductivity of h-BN itself and the improvement of the ionic conductivity of the composite may be due to the distortion of the BH bond of LiBH 4 caused by the amorphous h-BN, resulting in the amorphization of LiBH 4 , the interaction between the two amorphous phases The amorphous interface forms a fast channel for lithium ion migration.
  • it may hinder the migration of lithium ions and cause a decrease in ion conductivity; when there is more LiBH 4 , the relative amount of LiBH 4 amorphous is small, and the formed lithium Less fast pathways for ion migration lead to lower ionic conductivity.
  • the molar ratio is 1:2
  • the ionic conductivity of the composite system can reach 1.22 ⁇ 10 -4 S cm -1 at 30°C.
  • the ionic conductivity of the composite is poor compared to the molar ratio of 1:2.
  • the improvement of lithium ion mobility is mainly due to the formation of a fast lithium ion migration channel at the interface between crystal form 3LiBH 4 -LiI and amorphous h-BN.
  • the samples in this example are LiBH 4 -2BN and (3LiBH 4 -LiI)-2BN prepared in Example 1 and Example 2.
  • the electrochemical stability test of the samples was obtained by the cyclic voltammetry test method on the electrochemical workstation, and the stainless steel sheet was used as the working electrode, and the lithium metal foil was used as the counter electrode and the reference electrode to assemble an asymmetric battery.
  • the potential was swept from ⁇ 1 V to 5 V at a scan rate of 5 mV s ⁇ 1 , as shown in Fig. 11 and Fig. 12 .
  • no other peaks were observed, except two redox peaks around 0 V, which corresponded to the deposition and stripping of lithium on the stainless steel sheet, indicating that the composite electrolyte material has a broad electrochemical Stable window, with good electrochemical stability.
  • the ion mobility test of the sample was obtained by combining DC polarization and AC impedance on the electrochemical workstation.
  • the sample is pressed into a disc with a diameter of 10 mm and a thickness of about 1 mm with a pressure of 10-20 MPa.
  • the test battery was assembled according to the sandwich structure (lithium sheet/solid electrolyte sheet/lithium sheet), the DC polarization voltage was 10mV, and the AC impedance was tested before and after polarization.
  • the final ion mobility is 97%, indicating that lithium ions contribute almost all of the charge transfer, and the composite material is an excellent lithium ion transport conductor.
  • ⁇ V is the polarization voltage
  • the electronic conductivity performance test of the sample is obtained by the DC polarization test method on the electrochemical workstation.
  • the sample is pressed into a disc with a diameter of 10 mm and a thickness of about 1 mm with a pressure of 10-20 MPa.
  • sandwich structure stainless steel sheet/solid electrolyte sheet/stainless steel sheet
  • two stainless steel sheets were placed on both sides of the sample disc as electrodes, and the polarization voltage of DC polarization was 5V, as shown in Figure 15 and Figure 16.
  • the final steady-state currents are 1.80 ⁇ 10 -8 A and 3.97 ⁇ 10 -8 A, corresponding to electronic conductivities of 4.59 ⁇ 10 -10 S cm -1 and 1.01 ⁇ 10 -9 S cm -1 , and the average specific ionic conductivities is six orders of magnitude lower, indicating that in the complex, the migration of electrons is negligible and the migration of ions dominates.
  • the stability of the sample to lithium is obtained by constant current cycle test on the battery test cabinet.
  • the sample is pressed into a disc with a diameter of 10 mm and a thickness of about 1 mm with a pressure of 10-20 MPa.
  • LiBH 4 -2BN and (3LiBH 4 -LiI)-2BN can still cycle stably after more than 500 and 1100 hours of cycling respectively, indicating that the samples have excellent lithium stability.
  • the critical current density of the sample is obtained by increasing the current cycle test on the battery test cabinet.
  • the sample is pressed into a disc with a diameter of 10 mm and a thickness of about 1 mm with a pressure of 10-20 MPa.
  • Assemble a symmetrical battery (lithium sheet/solid electrolyte sheet/lithium sheet), select the current density to gradually increase from 0.05mAcm -2 to 10mAcm -2 , keep the total power equal, and the current density when the voltage drop occurs is the critical current density of the sample .
  • the critical current density of the sample can reflect the lithium dendrite suppression ability of the sample.
  • the critical current densities of LiBH 4 -2BN and (3LiBH 4 -LiI)-2BN are 4.6 mAcm -2 and 5.8 mAcm -2 , respectively, indicating that the samples have excellent lithium dendrite suppression ability .
  • the constant current cycle test of the TiS 2 -Li all-solid-state battery of the LiBH 4 -2BN sample was obtained by the constant current cycle test on the battery test cabinet.
  • the sample is pressed into a disc with a diameter of 10 mm and a thickness of about 0.5 mm at a pressure of 10-15 MPa, and then compounded with 40wt% TiS 2 -60wt% (LiBH 4 -2BN) at a pressure of 20-30 MPa
  • the cathode material is pressed on the LiBH 4 -2BN composite electrolyte sheet with a thickness of about 0.1 mm.

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Abstract

本发明公开了一种复合固态电解质材料及其制备方法和应用，电解质材料具有无定形与异质结混合界面；化学组成为(xLiBH 4-yLiI)-zBN，其中x、y、z为摩尔比，且1≤x≤5，0≤y≤5，1≤z≤5。制备方法为在惰性气体气氛下，先将一定量的h-BN预球磨，而后与xLiBH 4-yLiI以一定摩尔比混合后球磨，再在一定氢压下进行热处理。本发明的材料有优异的室温离子电导率、宽的电化学窗口、高锂离子迁移率、几乎可以忽略的电子电导率、极佳的电极兼容性、极强的锂枝晶抑制能力、优异的全固态电池性能。此材料是一种室温(T＜100℃)性能优越的锂离子导体，可以用作全固态锂离子电池的固态电解质。

Description

一种复合固态电解质材料及其制备方法和应用 技术领域
本发明属于固态电解质材料，具体涉及一种具有无定形和异质结界面的(xLiBH 4-yLiI)-zBN复合固态电解质材料及其制备方法和应用。
背景技术
锂离子二次电池以其高能量和功率密度、长寿命、环保等特点得到了广泛的应用，特别是在电动汽车和便携式设备上。传统的锂离子电池倾向于使用具有高离子导电性的有机液态电解质，但由于其挥发性、可燃性和易形成锂枝晶，会导致可逆容量衰减和严重的安全问题。这些问题长期以来一直阻碍着锂电池的发展。而使用固态电解质可以提高锂电池的安全性和性能，并且以其代替传统的锂电池中电解液和隔膜可实现系统的简单化和材料高效利用。氧化物和硫化物基固态电解质具有与液态电解质相似或稍低的离子电导率，但稳定性和电极相容性不能满足全固态锂电池的要求。LiBH 4是一种配位金属氢化物，其作为固态电解质具有宽的电化学窗口并且与大多数电极相容，主要缺点是室温电导率较低(＜10 -7S cm -1)。因此如何降低LiBH 4体系的相转变温度，最终可以使其在室温下稳定高温相，以适配全固态锂离子电池的固态电解质要求是亟需研究的方向。
发明内容
发明目的：本发明的目的在于提供一种由硼氢化物与六方氮化硼复合形成无定形与异质结混合界面的复合固态电解质材料；本发明的第二目的在于提供上述复合固态电解质材料的制备方法；本发明的第三目的在于提供上述复合固态电解质材料在制备电池电解质中的应用。
技术方案：本发明的一种复合固态电解质材料，所述电解质材料具有无定形与异质结混合界面；化学组成为(xLiBH 4-yLiI)-zBN，其中x、y、z为摩尔比，且1≤x≤5，0≤y≤5，1≤z≤5。
进一步的，所述(xLiBH 4-yLiI)-zBN中，x＝1，y＝0，z＝2或x＝3，y＝1，z＝2。
进一步的，所述电解质材料的低温离子电导率为(0.61-4.21)×10 -4Scm -1；其中，低温范围为30-50摄氏度。
上述的复合固态电解质材料的制备方法，包括以下步骤：
(1)将六方氮化硼在惰性气氛保护下进行高能球磨处理制备含无定形结构的六方氮化硼；
(2)将硼氢化锂与碘化锂在惰性气氛保护下进行高能球磨处理，而后在一定氢压下进行热处理制备得到xLiBH 4-yLiI固溶体；
(3)将含无定形界面的六方氮化硼与xLiBH 4-yLiI固溶体在惰性气氛保护下进行高能球磨处理得到(xLiBH 4-yLiI)-zBN混合物；
(4)将步骤(3)高能球磨后的混合物氢压下进行热处理制备得到含无定形和异质结界面的(xLiBH 4-yLiI)-zBN复合固态电解质。
进一步的，所述步骤(1)中，高能球磨的球料比为(40-45)：1，转速为450-550转/分钟，球磨时间为5～20小时。
进一步的，所述步骤(2)中，高能球磨的球料比为(40-45)：1，转速为500-550转/分钟，球磨时间为2-5小时。
进一步的，所述步骤(2)中，热处理的氢压为2-10兆帕，热处理温度为270-300摄氏度，升温速率为2-10摄氏度/分钟，保温时间为6-12小时。
进一步的，所述步骤(3)中，高能球磨的球料比为(40-45)：1，转速为400-500转/分钟，球磨时间为5-10小时。
进一步的，所述步骤(4)中，热处理的氢压为2-10兆帕，热处理温度为150-340摄氏度，升温速率为2-10摄氏度/分钟，保温时间为2-24小时。
上述复合固态电解质材料可以用作制备锂离子电池的固态电解质。
本发明的制备原理：通过硼氢化物与六方氮化硼构建了包含异质结和无定形结构的复合界面；六方氮化硼在球磨处理下产生部分缺陷并无定形化，在热处理过程中，六方氮化硼造成硼氢化物中的B-H键畸变导致硼氢化物无定形化，两个无定形相之间的无定形界面形成锂离子迁移快速通道，提高促进了低温下的离子电导率；同时，硼氢化物与六方氮化硼之间也存在晶相间的接触，形成了异质结结构，有助于电子分离，提高固态电池性能。
有益效果：与现有技术相比，本发明的具有如下显著优点：
(1)本发明制备的复合材料在低温下离子电导率约比LiBH 4高3～4个数量级，尤其在30-50摄氏度内可以达到10 -4S cm -1；且具有较宽的电化学稳定窗口(-1-5V vs.Li +)，高锂离子迁移率(97％)，几乎可以忽略的电子电导率(10 -10-10 -9S cm -1)，是优良的锂离子导体。
(2)本发明制备的复合物可以恒电流对锂稳定循环500小时以上，与锂电极具有良好相容性和电化学稳定性；临界电流密度4.6mA cm -2以上，展现出极强的锂枝晶抑制能力。
(3)本发明制备的复合物可以组装成TiS 2-Li全固态电池，TiS 2-Li全固态电池循环10圈后容量保持率可达93％，可以用作全固态锂离子电池的固态电解质，具有商业化应用价值。
附图说明
图1为预处理BN、纯LiBH 4和LiBH 4-zBN(z＝1,2,3)的X射线衍射图谱对比；
图2为球磨及热处理制得的材料LiBH 4-zBN(z＝1,2,3)的X射线衍射图谱；
图3为预处理BN、纯LiBH 4、3LiBH 4-LiI和(3LiBH 4-LiI)-2BN的X射线衍射图谱对比；
图4为球磨及热处理制得的材料(3LiBH 4-LiI)-zBN(z＝1,2,3,4,5)的X射线衍射图谱；
图5为球磨及热处理制得的材料LiBH 4-zBN(z＝1,2,3)的傅里叶变换红外光谱图；
图6为球磨及热处理制得的材料(3LiBH 4-LiI)-2BN的傅里叶变换红外光谱图；
图7为球磨及热处理制得的材料LiBH 4-2BN的界面高分辨透射电子显微镜照片；
图8为球磨及热处理制得的材料(3LiBH 4-LiI)-2BN的界面高分辨透射电子显微镜照片；
图9为球磨及热处理制得的材料LiBH 4-zBN(z＝1,2,3)的电导率随温度变化曲线；
图10为球磨及热处理制得的材料(3LiBH 4-LiI)-zBN(z＝1,2,3,4,5)的电导率随温度变化曲线；
图11为球磨及热处理制得的材料LiBH 4-2BN的循环伏安曲线；
图12为球磨及热处理制得的材料(3LiBH 4-LiI)-2BN的循环伏安曲线；
图13为球磨及热处理制得的材料LiBH 4-2BN的离子迁移率图；
图14为球磨及热处理制得的材料(3LiBH 4-LiI)-2BN的离子迁移率图；
图15为球磨及热处理制得的材料LiBH 4-2BN的电子电导率图；
图16为球磨及热处理制得的材料(3LiBH 4-LiI)-2BN的电子电导率图；
图17为球磨及热处理制得的材料LiBH 4-2BN的恒电流对锂循环图；
图18为球磨及热处理制得的材料(3LiBH 4-LiI)-2BN的恒电流对锂循环图；
图19为球磨及热处理制得的材料LiBH 4-2BN的增电流对锂循环图；
图20为球磨及热处理制得的材料(3LiBH 4-LiI)-2BN的增电流对锂循环图；
图21为球磨及热处理制得的材料LiBH 4-2BN组装成的TiS2-Li电池恒流充放电曲线及循环图。
具体实施方式
下面结合附图和实施例对本发明的技术方案做进一步详细说明。
以LiBH 4-zBN(z＝1,2,3)和(3LiBH 4-LiI)-zBN(z＝1,2,3,4,5)为例，为避免其它副反应，所有的样品操作均在充有高纯氩气的手套箱中进行，手套箱的氧气和水含量均低于1ppm浓度。
实施例1
(1)在隔绝空气(H 2O<1ppm，O 2<1ppm)条件下，将0.5g的六方氮化硼放入装有不锈钢磨球的不锈钢球罐中；采用行星轮式球磨机机械球磨方式，在高纯度(99.9999％)惰性气体(氩气)保护下，获得含无定形结构的六方氮化硼。球磨罐容积为100毫升，磨球与样品的重量比为40：1，球磨时间为10小时，公转转速设定为500转/分钟。
(2)将无定形结构的六方氮化硼与硼氢化锂分别按照1：1、1：2和1：3的摩尔比计算质量，称取后再次放入装有不锈钢磨球的球罐中；采用行星轮式球磨机机械球磨方式，在高纯度(99.9999％)惰性气体(氩气)保护下，获得含无定形结构的六方氮化硼与硼氢化锂的混合物。球罐中样品总质量为0.5克，球磨罐容积为100毫升，磨球与样品的重量比为40：1，球磨时间为5小时，公转转速设定为450转/分钟。将球磨获得的混合物装入Sievert型气固反应P-C-T装置，在一定氢压下热处理得到LiBN 4-zBN复合物，z＝1，2，3；热处理过程中，氢气压力为4兆帕，热处理温度为295摄氏度，升温速率为10摄氏度/分钟，保温时间为24小时。
实施例2
(1)在隔绝空气(H 2O<1ppm，O 2<1ppm)条件下，将0.5g的六方氮化硼放入装有不锈钢磨球的不锈钢球罐中；采用行星轮式球磨机机械球磨方式，在高纯度(99.9999％)惰性气体(氩气)保护下，获得含无定形结构的六方氮化硼。球磨罐容积为100毫升，磨球与样品的重量比为45：1，球磨时间为20小时，公转转速设定为450转/分钟
(2)在隔绝空气(H 2O<1ppm，O 2<1ppm)条件下，将0.3360g的LiI与0.1640g的LiBH 4放入装有不锈钢磨球的不锈钢球罐中；采用行星轮式球磨机机械球磨方式，在高纯度(99.9999％)惰性气体(氩气)保护下，获得LiBH 4与LiI的混合物。球磨罐容积为100毫升，磨球与样品的重量比为40：1，球磨时间为4小时，公转转速设定为510转/分钟。而后，将LiBH 4与LiI的混合物装入Sievert型气固反应P-C-T装置，在一定氢压下热处理得到3LiBH 4-LiI固溶体。热处理过程中，氢气压力为4兆帕，热处理温度为275摄氏度，升温速率为6摄氏度/分钟，保温时间为12小时。
(3)将含无定形结构的的六方氮化硼与3LiBH 4-LiI按照1：1、1：2、1：3、 1：4和1：5的摩尔比计算质量，称取后再次放入装有不锈钢磨球的球罐中；采用行星轮式球磨机机械球磨方式，在高纯度(99.9999％)惰性气体(氩气)保护下，获得含无定形和异质结界面的六方氮化硼与3LiBH 4-LiI的混合物。球罐中样品总质量为0.5克，球磨罐容积为100毫升，磨球与样品的重量比为40：1，球磨时间为10小时，公转转速设定为450转/分钟。最后，将球磨获得的混合物压成电解质片装入Sievert型气固反应P-C-T装置，在一定氢压下热处理得到(3LiBH 4-LiI)-zBN复合物，z＝1，2，3，4，5。热处理过程中，氢气压力为8兆帕，热处理温度为150摄氏度，升温速率为2摄氏度/分钟，保温时间为2小时。
实施例3
取实施例1制备的LiBH 4-zBN，z＝1，2，3和实施例2制备的(3LiBH 4-LiI)-zBN，z＝1，2，3，4，5进行X射线衍射(XRD)实验，样品池被特定高分子膜覆盖，并以真空脂将其与载玻片密封，以阻止空气中水和氧气对样品的作用。所用X射线源的靶材为Cu靶，管电压为40kV，管电流为40mA。
参见图1和图2，球磨及热处理后的LiBH 4-zBN复合物(z＝1,2,3)中，预先球磨的h-BN相峰位没有发生变化，峰强相较球磨之前有所减弱，说明有部分无定形化；LiBH 4相同样峰位没有变化，峰强有所减弱，说明同样有部分无定形化。产物没有中间相生成，说明制备过程中LiBH 4与h-BN没有发生相互反应也没有经历自分解。
参见图3和图4，球磨及热处理后的(3LiBH 4-LiI)-zBN复合物(z＝1,2,3,4,5)中，3LiBH 4-LiI与h-BN复合后，与3LiBH 4-LiI相比，峰位和峰强几乎没有变化，说明3LiBH 4-LiI与h-BN间化学稳定。同时，3LiBH 4-LiI依旧保持晶态而h-BN完全无定形化。
实施例4
取出实施例1和实施例2中不同摩尔比的部分LiBH 4-zBN和(3LiBH 4-LiI)-2BN复合物颗粒进行傅里叶红外光谱(FTIR)测试，因实验样品必须与空气隔绝，所以制备全程在手套箱中进行。按质量比，样品粉末：KBr粉末＝1:200的比例，混合两种粉末，研磨均匀。制备好的粉末装入棕色的小玻璃瓶中保存。在FTIR测试前，把粉末样品从玻璃瓶中取出，取适量粉末放入压片模具中，在20MPa压强下，压1分钟，然后卸压30秒，再压1分钟，得到片状测试样品。
从图5中可以看出，LiBH 4-zBN复合物(z＝1,2,3)中，存在LiBH 4的B-H振动带，2300cm -1处的伸缩ν振动带和1320cm -1剪切δ振动带；也存在h-BN的B-N振动带，1373cm -1的伸缩ν振动带和797cm -1的弯曲γ振动带。值得注意的 是，在波数968cm -1处，在B-H键范围内有一个小的吸收峰，可能对应h-BN与LiBH 4中B-H键的相互作用，导致LiBH 4中B-H键出现畸变。
从图6中可以看出，(3LiBH 4-LiI)-2BN复合物中，存在(3LiBH 4-LiI)的B-H振动带，2300cm -1处的伸缩ν振动带和1320cm -1剪切δ振动带；也存在h-BN的B-N振动带，1373cm -1的伸缩ν振动带和797cm -1的弯曲γ振动带。值得注意的是，(3LiBH 4-LiI)-2BN与3LiBH 4-LiI在波数968cm -1处，在B-H键范围内都有一个小的吸收峰，说明h-BN与3LiBH 4-LiI中的B-H键和I -三者之间存在相互作用。
实施例5
取出微量的实施例1的LiBH 4-2BN复合物颗粒和实施例2的(3LiBH 4-LiI)-2BN复合物颗粒，利用高分辨率透射式电子显微镜对其进行微观形貌及相结构的分析，将微量的复合物颗粒与酒精混合，超声分散两分钟，使其均匀分散，然后吸取微量混合液滴到铜网上即可进行测试。
从图7中可以看出，较亮的LiBH 4颗粒分散在h-BN薄片上，同时LiBH 4-2BN复合物呈现的无序结构以及傅里叶变换(FFT)图像中的色散环说明了LiBH 4和h-BN的无定形化以及它们之间的无定形界面层的存在。另外，LiBH 4与h-BN之间也存在晶相间的接触，形成了异质结结构。
参见图8，其中，从a中可以看出，晶型3LiBH 4-LiI颗粒分散在无定形h-BN上，b证实了3LiBH 4-LiI的晶型结构。而d为STEM-HAADF，同样可以证实较亮的3LiBH 4-LiI颗粒分散在h-BN薄片上。
实施例6
样品的离子电导率性能测试是在电化学工作站上以交流阻抗测试方法获得的。将实施例1和实施例2所获得的样品以10～20兆帕的压强压制成一个直径10毫米，厚度约1毫米的圆片。按照三明治结构(锂片/固态电解质片/锂片)，将两块锂箔片放置在样品圆片的两面作为电极。再以1～10吨/平方厘米的压力将锂箔片与样品片压紧致。所有的制备都在高纯氩气(99.9999％)下进行。交流阻抗测试的频率范围是从1MHz到1Hz。样品以2摄氏度/分钟的速度升温，每间隔5-10℃采集一次阻抗谱。温度由室温升至120摄氏度。通过获得的交流阻抗Nyquist谱图和Zview进行拟合得到离子电导率，并可作出电导率随温度的变化曲线。
参见图9，与纯LiBH 4相比，LiBH 4-zBN复合物(z＝1,2,3)均表现出比LiBH 4更高的离子电导率，尤其是在低温范围内。当摩尔比为1:2时，复合材料的离子电导率在40摄氏度可达到10 -4S cm -1数量级。而当h-BN过多或过少(x:y＝1:1或1:3)时，复合材料的离子电导率相较摩尔比为1:2较差。由于h-BN本身极差的离子电导率并且复合物离子电导率的提升可能源于无定形的h-BN造成LiBH 4 的B-H键畸变导致LiBH 4无定形化，两个无定形相之间的无定形界面形成锂离子迁移快速通道，当h-BN过多时，可能会阻碍锂离子的迁移造成离子电导率降低；而LiBH 4较多时，LiBH 4无定形化的相对数量较少，形成的锂离子迁移快速通道较少导致离子电导率降低。
参见图10，与3LiBH 4-LiI相比，(3LiBH 4-LiI)-zBN复合物(z＝1,2,3,4,5)均表现出比3LiBH 4-LiI和LiBH 4-2BN更高的离子电导率。当摩尔比为1:2时，复合体系的离子电导率在30摄氏度可达到1.22×10 -4S cm -1。当h-BN过多或过少(z＝1,3,4,5)时，复合材料的离子电导率相较摩尔比为1:2较差。在本体系中，锂离子迁移率的提升主要归因于晶型3LiBH 4-LiI与无定形h-BN界面处形成了锂离子迁移快速通道，由于h-BN较差的离子电导率，当h-BN过多时，会造成体系离子电导率的下降，而3LiBH 4-LiI过多时又无法形成足够的连续的复合界面快速迁移通道，同样造成体系离子电导率的下降。
实施例7
该实施例的样品为实施例1和实施例2制备的LiBH 4-2BN和(3LiBH 4-LiI)-2BN。
样品的电化学稳定性试是在电化学工作站上以循环伏安的测试方法获得的，以不锈钢片作为工作电极，锂金属箔片作为对电极和参比电极组装不对称电池。电势以5mV s -1的扫描速率从-1V扫至5V，如图11和图12所示。在起始的三个循环中，没有观察到其他的峰，除了在0V左右的两个氧化还原峰，其对应锂在不锈钢片上的沉积与剥离，表明了该复合电解质材料具有较宽的电化学稳定窗口，具有良好的电化学稳定性。
样品的离子迁移率测试是在电化学工作站上以直流极化和交流阻抗相结合的测试方法获得的。将样品以10～20兆帕的压强压制成一个直径10毫米，厚度约1毫米的圆片。按照三明治结构(锂片/固态电解质片/锂片)装配测试电池，直流极化电压为10mV，极化前后分别测试其交流阻抗。如图13和图14所示，最终可得到其离子迁移率均为97％，表明了锂离子贡献了几乎全部的电荷转移，复合材料为极佳的锂离子传输导体，
离子迁移数的计算公式如下：
Figure PCTCN2022098509-appb-000001
其中，△V为极化电压，I(t＝0)为起始电流，I(t＝∞)为终态电流，R(t＝0)为极化前的电阻，R(t＝∞)为极化后的电阻。
样品的电子电导率性能测试是在电化学工作站上以直流极化的测试方法获 得的。将样品以10～20兆帕的压强压制成一个直径10毫米，厚度约1毫米的圆片。按照三明治结构(不锈钢片/固态电解质片/不锈钢片)，将两块不锈钢片放置在样品圆片的两面作为电极，直流极化的极化电压为5V，如图15和图16所示。最终的稳态电流为1.80×10 -8A和3.97×10 -8A，对应电子电导率为4.59×10 -10S cm -1和1.01×10 -9S cm -1，均比离子电导率低了六个数量级，表明在复合物中，电子的迁移是可以忽略的，离子迁移是主体。
样品的对锂稳定性是在电池测试柜上以恒电流循环测试获得的。将样品以10～20兆帕的压强压制成一个直径10毫米，厚度约1毫米的圆片。装配对称电池(锂片/固态电解质片/锂片)，选用恒电流密度为0.5mAcm -2。如图17和图18所示，LiBH 4-2BN和(3LiBH 4-LiI)-2BN在分别经历了500和1100多个小时的循环后，依旧可以稳定循环，表明了该样品具有优异的对锂稳定性。
样品的临界电流密度是在电池测试柜上以增电流循环测试获得的。将样品以10～20兆帕的压强压制成一个直径10毫米，厚度约1毫米的圆片。装配对称电池(锂片/固态电解质片/锂片)，选用电流密度从0.05mAcm -2逐渐增加至10mAcm -2，保持总电量相等，电压突降出现时的电流密度便是样品的临界电流密度。样品的临界电流密度可以反映样品的锂枝晶抑制能力。如图19和图20所示，LiBH 4-2BN和(3LiBH 4-LiI)-2BN的临界电流密度分别为4.6mAcm -2和5.8mAcm -2，表明了该样品具有优异的锂枝晶抑制能力。
LiBH 4-2BN样品的TiS 2-Li全固态电池恒电流循环测试是在电池测试柜上以恒电流循环测试获得的。将样品以10～15兆帕的压强压制成一个直径10毫米，厚度约0.5毫米的圆片，而后再以20～30兆帕的压强将40wt％TiS 2-60wt％(LiBH 4-2BN)复合正极材料压制在LiBH 4-2BN复合电解质片上，厚度约0.1毫米。然后转配成全固态电池((40wt％TiS 2-60wt％(LiBH 4-2BN))|LiBH 4-2BN|Li)，选用恒电流密度为0.1mAcm -2。如图21所示，经过10个循环后，全电池容量保持率为93％。

Claims (10)

  1. 一种复合固态电解质材料，其特征在于：所述电解质材料具有无定形与异质结混合界面；化学组成为(xLiBH 4-yLiI)-zBN，其中x、y、z为摩尔比，且1≤x≤5，0≤y≤5，1≤z≤5。
  2. 根据权利要求1所述的一种复合固态电解质材料，其特征在于：所述(xLiBH 4-yLiI)-zBN中，x＝1，y＝0，z＝2或x＝3，y＝1，z＝2。
  3. 根据权利要求1所述的一种复合固态电解质材料，其特征在于：所述电解质材料的低温离子电导率为(0.61-4.21)×10 -4Scm -1；其中，低温范围为30-50摄氏度。
  4. 一种权利要求1所述的复合固态电解质材料的制备方法，其特征在于，包括以下步骤：
    (1)将六方氮化硼在惰性气氛保护下进行高能球磨处理制备含无定形结构的六方氮化硼；
    (2)将硼氢化锂与碘化锂在惰性气氛保护下进行高能球磨处理，而后在一定氢压下进行热处理制备得到xLiBH 4-yLiI固溶体；
    (3)将含无定形界面的六方氮化硼与xLiBH 4-yLiI固溶体在惰性气氛保护下进行高能球磨处理得到(xLiBH 4-yLiI)-zBN混合物；
    (4)将步骤(3)高能球磨后的混合物氢压下进行热处理制备得到含无定形和异质结界面的(xLiBH 4-yLiI)-zBN复合固态电解质。
  5. 根据权利要求4所述的复合固态电解质材料的制备方法，其特征在于：所述步骤(1)中，高能球磨的球料比为(40-45)：1，转速为450-550转/分钟，球磨时间为5～20小时。
  6. 根据权利要求4所述的复合固态电解质材料的制备方法，其特征在于：所述步骤(2)中，高能球磨的球料比为(40-45)：1，转速为500-550转/分钟，球磨时间为2-5小时。
  7. 根据权利要求4所述的复合固态电解质材料的制备方法，其特征在于：所述步骤(2)中，热处理的氢压为2-10兆帕，热处理温度为270-300摄氏度，升温速率为2-10摄氏度/分钟，保温时间为6-12小时。
  8. 根据权利要求4所述的复合固态电解质材料的制备方法，其特征在于：所述步骤(3)中，高能球磨的球料比为(40-45)：1，转速为400-500转/分钟，球磨时间为5-10小时。
  9. 根据权利要求4所述的复合固态电解质材料的制备方法，其特征在于：所述步骤(4)中，热处理的氢压为2-10兆帕，热处理温度为150-340摄氏度，升温速率为2-10摄氏度/分钟，保温时间为2-24小时。
  10. 权利要求1所述的复合固态电解质材料在制备锂离子电池电解质中的应用。
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