CN113394383B - 一种用于硫化物固态电池的正极材料的包覆方法 - Google Patents
一种用于硫化物固态电池的正极材料的包覆方法 Download PDFInfo
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000002243 precursor Substances 0.000 claims abstract description 57
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 239000010410 layer Substances 0.000 claims abstract description 26
- 239000011247 coating layer Substances 0.000 claims abstract description 17
- 239000010416 ion conductor Substances 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002203 sulfidic glass Substances 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 8
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 4
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910007786 Li2WO4 Inorganic materials 0.000 claims description 2
- 229910011201 Li7P3S11 Inorganic materials 0.000 claims description 2
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 20
- 238000000231 atomic layer deposition Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 239000003595 mist Substances 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910008029 Li-In Inorganic materials 0.000 description 1
- 229910006670 Li—In Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- -1 but not limited to Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
本发明公开一种用于硫化物固态电池的正极材料的包覆方法。该方法包括：(1)将正极材料放置于ALD设备的反应腔室中；(2)等待反应腔室温度达到第一设定值，通过惰性气体加载各前驱体源到反应腔室，在正极材料表面沉积一层快离子导体；(3)替换前驱体源，待反应腔室温度达到第二设定值，继续通过惰性气体加载硫化物电解质前驱体源到反应腔室，在快离子导体层表面沉积一层硫化物固态电解质；(4)包覆的正极材料直接在ALD反应腔室中退火，自然冷却后，即得到双层包覆的正极材料。本发明提供的方法流程简单，可自动化、连续性地在正极材料表面一步包覆双层包覆层，且沉积的包覆层均匀保形，厚度可控。
Description
技术领域
本发明属于锂离子电池技术领域，具体涉及一种用于硫化物固态电池的正极材料的包覆方法。
背景技术
全固态电池安全性高，能量密度高，工作温度窗口宽，是最有潜力的下一代储能器件之一。其中，硫化物固态电解质材料是实现高性能全固态电池的最有希望的材料。几种硫化物固态电解质的室温锂离子电导率高达10-2S cm-1，例如Li10GeP2S12，Li7P3S11，Li6PS5Cl等。将传统商业化正极材料LixMO2(M＝Co,Ni,Mn)、金属锂负极、硫化物固态电解质组装到全固态电池中，可获得更安全、更高能量密度和更稳定的锂离子电池。
但是，传统的LixMO2正极材料与硫化物固态电解质之间的界面不稳定性，导致了较大的界面电阻，降低了全固态电池的电化学性能。一方面，硫化物固态电解质的电化学稳定窗口有限，高氧化态的正极材料容易与电解质发生副反应，其界面还存在着空间电荷层效应、过渡金属的互扩散，晶格失配等问题；另一方面，环境气氛条件下制备的LixMO2正极材料，其表面一般会残存有害的LiOH和Li2CO3杂质。此外，硫化物固态电解质与正极颗粒之间较差的界面润湿性也限制了电池电化学性能的提升。
在正极颗粒表面包覆一层相对稳定的锂离子导体是稳定正极-电解质界面的有效策略。常用的包覆方法包括高能球磨的干法包覆法和溶液-沉积-烧结的湿法包覆法。其中，干法包覆得到的包覆层均匀性和完整性较差，且难以保证包覆成分的均一性；而湿法包覆的工艺繁琐，对包覆材料溶剂要求较高。特别是硫化物电解质层的包覆，传统的干法包覆不能保证包覆层的均匀和完整，通常电解质以粉末颗粒状附着在基体颗粒表面；而湿法包覆流程复杂，也很难保证重新结晶的硫化物电解质包覆均匀，通常需要添加其他添加剂，例如成膜剂或非极性溶剂以辅助硫化物电解质溶液沉积包覆在基体颗粒表面。上述方法都难以达到硫化物电解质的最佳的包覆效果。此外，上述传统的包覆方法每次只能实现一种包覆层的包覆，存在局限性。
发明内容
本发明的主要目的在于克服现有技术的不足，提供一种工艺流程简单，可自动化、连续性地在正极材料表面一步包覆双层包覆层的硫化物固态电池用正极材料的包覆方法。本发明通过原子层沉积技术(Atomic layer deposition,ALD)，依次连续地将快离子导体层和硫化物固态电解质层包覆在正极活性材料表面。其中，包覆层的各前驱体源通过惰性载气以脉冲的方式依次加载到反应腔室中。反应腔室中的正极颗粒在流化床功能的作用下翻涌，因此前驱体源均匀地沉积并完整覆盖在正极颗粒表面。同时，各前驱体源在一定温度下反应生成相应的包覆层。沉积的包覆层成分均一，厚度均匀可控，得到的包覆正极材料用于硫化物全固态电池，具有高安全性、高能量密度和优异的循环稳定性。
为实现上述目的，本发明提供的用于硫化物固态电池的正极材料的包覆方法包括以下步骤：
(1)将正极材料放置于ALD设备的反应腔室中；
(2)待反应腔室温度达到第一设定值，通过惰性气体加载各前驱体源到反应腔室，在正极材料表面沉积一层快离子导体，所述快离子导体包括Li3PO4、Li2WO4、Li3BO3中的一种或多种；
(3)替换前驱体源，待反应腔室温度达到第二设定值，继续通过惰性气体加载硫化物电解质前驱体源到反应腔室，在快离子导体包覆层表面沉积一层硫化物固态电解质，所述硫化物固态电解质包括Li6PS5-aOaX、Li3PS4或Li7P3S11中的一种或多种，其中，a＝0～1，X＝Cl、Br或I；
(4)包覆的正极材料直接在ALD反应腔室中退火，自然冷却后，即得到双层包覆的正极材料。
优选地，所述步骤(1)中的正极材料包括LiCoO2、Li(NiaCobXc)O2或LiMn2O4中的一种或多种，其中，a+b+c＝1，X＝Mn或Al。
优选地，所述步骤(1)中的反应腔室具有流化床功能。
优选地，当快离子导体为硼酸锂时，所述步骤(2)中的前驱体源包括锂源前驱体、硼源前驱体和氧源前驱体，所述锂源前驱体包括叔丁醇锂，硼源前驱体包括硼酸三乙酯，氧源前驱体包括H2O。
优选地，所述步骤(2)中的反应腔室的温度为50～500℃，腔室压力为0.5～1MPa。
优选地，所述步骤(2)中的前驱体源的脉冲循环次数为1～10000次，对应地，正极材料表面的快离子导体包覆层厚度为1μm以内。
优选地，所述步骤(3)中的前驱体源为硫化物电解质的有机稀溶液，包括0.001～0.1M Li6PS5X的乙醇溶液、0.001～0.1M Li6PS5Br0.5Cl0.5的乙醇溶液、0.001～0.1MLi6PS4.75O0.25Cl的乙醇溶液、0.001～0.2M Li3PS4的N-甲基甲酰胺溶液、0.001～0.1MLi7P3S11的乙腈溶液中的一种或多种，其中，X＝Cl、Br或I。
优选地，所述步骤(3)中的反应腔室的温度为50～300℃，腔室压力为0.5～1MPa。
优选地，所述步骤(3)中的前驱体源的脉冲循环次数为1～40000次，对应地，正极材料表面的硫化物电解质包覆层厚度为2μm以内。
优选地，所述步骤(4)中的退火的温度为300～600℃，保温时间为1～3小时。
优选地，所述步骤(2)(3)中的惰性载气包括但不限于氩气Ar、氮气N2；其他各步骤也在惰性气体保护下进行，所述惰性气体包括但不限于氩气Ar、氮气N2。
相对现有技术，本发明技术方案带来的有益效果如下：
(1)本发明通过惰性载气将前驱体源依次引入到翻滚的正极材料表面，同时前驱体源在一定温度下原位反应生成包覆层。得到的包覆层成分均一，厚度高度均匀，包覆完整，包覆效果比传统包覆技术好。此外，通过调整前驱体源的脉冲循环次数，可实现包覆层厚度的精准控制，可以使包覆正极材料具有最佳的电化学性能。
(2)特别是硫化物电解质的正极包覆，其前驱体源汽化后随惰性载气体加载并均匀沉积在包覆了快离子导体的正极颗粒表面，经一定温度退火后，微纳尺寸的硫化物电解质均匀且致密的包覆在正极表面。硫化物电解质的有效包覆可改善正极材料与硫化物电解质的接触性能，这将有利于提高复合正极中活性物质/硫化物电解质的比例，从而提高全固态电池的能量密度。
(3)本发明提供的包覆方法可以一步完成多层包覆，连续地将快离子导体层和硫化物固态电解质层包覆在正极活性材料表面上，克服了传统包覆方法每次只能包覆一层物质的缺陷，且工艺自动化控制，流程简单，适用于大规模工业化生产。
附图说明
图1为实施例1包覆的LiCoO2正极颗粒示意图。
具体实施方式
下面结合附图和实施例对本发明作进一步的详细说明。可以理解的是，此处所描述的具体实施例仅仅用于解释本发明，而非对本发明的限定。
实施例1：
将5kg LiCoO2正极材料放置于ALD设备的反应腔室中，待反应腔室温度达到350℃，依次按照Li2WO4各元素的化学计量比加载前驱体源叔丁醇锂C4H9LiO、六羰基钨W(CO)6、H2O到反应腔室中。其中，腔室压力为0.7mbar，前驱体源脉冲循环次数为200次。替换硫化物电解质的前驱体源，待反应腔室温度达到200℃，继续通过惰性气体加载0.05M Li3PS4的N-甲基甲酰胺溶液的汽化雾到反应腔室。其中，腔室压力为0.8mbar，前驱体源脉冲循环次数为1000次。硫化物电解质包覆工序结束后，提高反应腔室的温度到400℃，使包覆的正极材料直接在ALD反应腔室中退火，自然冷却后，即得到双层包覆的LiCoO2正极材料。
实施例2：
将5kg LiNi0.8Co0.1Mn0.1O2正极材料放置于ALD设备的反应腔室中，待反应腔室温度达到300℃，依次按照Li3BO3各元素的化学计量比加载前驱体源叔丁醇锂C4H9LiO、硼酸三乙酯C6H15BO3、H2O到反应腔室中。其中，腔室压力为0.7mbar，前驱体源脉冲循环次数为200次。替换硫化物电解质的前驱体源，待反应腔室温度达到100℃，继续通过惰性气体加载0.01M Li6PS5Cl的乙醇溶液的汽化雾到反应腔室。其中，腔室压力为0.8mbar，前驱体源脉冲循环次数为5000次。硫化物电解质包覆工序结束后，提高反应腔室的温度到450℃，使包覆的正极材料直接在ALD反应腔室中退火，自然冷却后，即得到双层包覆的LiNi0.8Co0.1Mn0.1O2正极材料。
实施例3：
将5kg LiNi0.6Co0.2Mn0.2O2正极材料放置于ALD设备的反应腔室中，待反应腔室温度达到300℃，依次按照Li3PO4各元素的化学计量比加载前驱体源叔丁醇锂C4H9LiO、磷酸三乙酯C6H15O4P、H2O到反应腔室中。其中，腔室压力为0.7mbar，前驱体源脉冲循环次数为200次。替换硫化物电解质的前驱体源，待反应腔室温度达到100℃，继续通过惰性气体加载0.01M Li7P3S11的乙腈溶液的汽化雾到反应腔室。其中，腔室压力为0.8mbar，前驱体源脉冲循环次数为5000次。硫化物电解质包覆工序结束后，提高反应腔室的温度到450℃，使包覆的正极材料直接在ALD反应腔室中退火，自然冷却后，即得到双层包覆的LiNi0.6Co0.2Mn0.2O2正极材料。
实施例4：
将5kg LiNi0.8Co0.15Al0.05O2正极材料放置于ALD设备的反应腔室中，待反应腔室温度达到350℃，依次按照Li2WO4各元素的化学计量比加载前驱体源叔丁醇锂C4H9LiO、六羰基钨W(CO)6、H2O到反应腔室中。其中，腔室压力为0.7mbar，前驱体源脉冲循环次数为200次。替换硫化物电解质的前驱体源，待反应腔室温度达到100℃，继续通过惰性气体加载0.01MLi6PS4.75O0.25Cl的乙醇溶液的汽化雾到反应腔室。其中，腔室压力为0.8mbar，前驱体源脉冲循环次数为5000次。硫化物电解质包覆工序结束后，提高反应腔室的温度到450℃，使包覆的正极材料直接在ALD反应腔室中退火，自然冷却后，即得到双层包覆的LiNi0.8Co0.15Al0.05O2正极材料。
按照质量比80：17：3称取实施例1～4中制备的包覆正极材料、包覆正极的硫化物电解质、VGCF导电碳，研磨10min制备复合正极。作为对比项，以同样的方法制备以未包覆正极材料作为活性物质的复合正极。将实施例1～4制备的复合正极以及相应的对比项复合正极压制到直径为10mm的电解质片上，以Li-In合金作为负极，组装全固态电池并进行电化学性能测试。测试条件为：电流0.3C倍率，电压范围3.0～4.3V(vs.Li+/Li)，循环100周。测试结果参考下表1：
表1实施例1-4电化学性能测试结果
实施例5：
将5kg LiMn2O4正极材料放置于ALD设备的反应腔室中，待反应腔室温度达到300℃，依次按照Li3PO4各元素的化学计量比加载前驱体源叔丁醇锂C4H9LiO、磷酸三乙酯C6H15O4P、H2O到反应腔室中。其中，腔室压力为0.7mbar，前驱体源脉冲循环次数为200次。替换硫化物电解质的前驱体源，待反应腔室温度达到100℃，继续通过惰性气体加载0.008MLi6PS5Br的乙醇溶液的汽化雾到反应腔室。其中，腔室压力为0.8mbar，前驱体源脉冲循环次数为5300次。硫化物电解质包覆工序结束后，提高反应腔室的温度到450℃，使包覆的正极材料直接在ALD反应腔室中退火，自然冷却后，即得到双层包覆的LiMn2O4正极材料。
实施例6：
将5kg LiNi0.9Co0.05Al0.05O2正极材料放置于ALD设备的反应腔室中，待反应腔室温度达到300℃，依次按照Li3BO3各元素的化学计量比加载前驱体源叔丁醇锂C4H9LiO、硼酸三乙酯C6H15BO3、H2O到反应腔室中。其中，腔室压力为0.7mbar，前驱体源脉冲循环次数为200次。替换硫化物电解质的前驱体源，待反应腔室温度达到100℃，继续通过惰性气体加载0.008M Li6PS5Br0.5Cl0.5的乙醇溶液的汽化雾到反应腔室。其中，腔室压力为0.8mbar，前驱体源脉冲循环次数为5300次。硫化物电解质包覆工序结束后，提高反应腔室的温度到450℃，使包覆的正极材料直接在ALD反应腔室中退火，自然冷却后，即得到双层包覆的LiNi0.9Co0.05Al0.05O2正极材料。
Claims (8)
1.一种用于硫化物固态电池的正极材料的包覆方法，其特征在于，所述的包覆方法包括以下步骤：
(1)将正极材料放置于ALD设备的反应腔室中，所述正极材料包括LiCoO2、Li(NiaCobXc)O2、LiMn2O4中的一种或多种，a+b+c＝1，X＝Mn或Al；
(2)待反应腔室温度达到第一设定值，通过惰性气体加载各前驱体源到反应腔室，在正极材料表面沉积一层快离子导体，所述快离子导体包括Li3PO4、Li2WO4、Li3BO3中的一种或多种；
(3)替换前驱体源，待反应腔室温度达到第二设定值，继续通过惰性气体加载硫化物电解质前驱体源到反应腔室，在快离子导体包覆层表面沉积一层硫化物固态电解质，所述硫化物固态电解质包括Li6PS5-aOaX、Li3PS4、Li7P3S11中的一种或多种，a＝0～1，X＝Cl、Br或I，所述硫化物电解质前驱体源为硫化物电解质的有机稀溶液，包括0.001～0.1M Li6PS5X的乙醇溶液、0.001～0.1M Li6PS5Br0.5Cl0.5的乙醇溶液、0.001～0.1M Li6PS4.75O0.25Cl的乙醇溶液、0.001～0.2MLi3PS4的N-甲基甲酰胺溶液、0.001～0.1M Li7P3S11的乙腈溶液中的一种或多种，X＝Cl、Br或I；
(4)包覆的正极材料直接在ALD反应腔室中退火，自然冷却后，即得到双层包覆的正极材料。
2.根据权利要求1所述的用于硫化物固态电池的正极材料的包覆方法，其特征在于，所述步骤(1)中的反应腔室具有流化床功能。
3.根据权利要求1所述的用于硫化物固态电池的正极材料的包覆方法，其特征在于，当快离子导体为硼酸锂时，所述步骤(2)中的前驱体源包括锂源前驱体、硼源前驱体和氧源前驱体，所述锂源前驱体包括叔丁醇锂，硼源前驱体包括硼酸三乙酯，氧源前驱体包括H2O。
4.根据权利要求1所述的用于硫化物固态电池的正极材料的包覆方法，其特征在于，所述步骤(2)中的反应腔室的温度为50～500℃，腔室压力为0.5～1MPa。
5.根据权利要求1所述的用于硫化物固态电池的正极材料的包覆方法，其特征在于，所述步骤(2)中的前驱体源的脉冲循环次数为1～10000次，对应地，正极材料表面的快离子导体包覆层厚度为1μm以内。
6.根据权利要求1所述的用于硫化物固态电池的正极材料的包覆方法，其特征在于，所述步骤(3)中的反应腔室的温度为50～300℃，腔室压力为0.5～1MPa。
7.根据权利要求1所述的用于硫化物固态电池的正极材料的包覆方法，其特征在于，所述步骤(3)中的前驱体源的脉冲循环次数为1～40000次，对应地，正极材料表面的硫化物电解质包覆层厚度为2μm以内。
8.根据权利要求1所述的用于硫化物固态电池的正极材料的包覆方法，其特征在于，所述步骤(4)中的退火的温度为300～600℃，保温时间为1～3小时。
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