WO2024021822A1 - Magnesium-based solid electrolyte, preparation method therefor, and battery - Google Patents

Magnesium-based solid electrolyte, preparation method therefor, and battery Download PDF

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Publication number
WO2024021822A1
WO2024021822A1 PCT/CN2023/096448 CN2023096448W WO2024021822A1 WO 2024021822 A1 WO2024021822 A1 WO 2024021822A1 CN 2023096448 W CN2023096448 W CN 2023096448W WO 2024021822 A1 WO2024021822 A1 WO 2024021822A1
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magnesium
solid electrolyte
based solid
source compound
powder material
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PCT/CN2023/096448
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French (fr)
Chinese (zh)
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申彤
李婷
沈德赟
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宜宾南木纳米科技有限公司
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Publication of WO2024021822A1 publication Critical patent/WO2024021822A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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

Definitions

  • the present invention relates to the technical field of new energy battery materials, and in particular to a magnesium-based solid electrolyte and its preparation method and battery.
  • magnesium is not as active as lithium and is easy to operate; it is pollution-free and has good safety. Low price, its price is only 1/24 of lithium. Therefore, carrying out research on magnesium-based materials in solid-state electrolytes can, on the one hand, alleviate the economic problems caused by the shortage of lithium raw materials; on the other hand, carrying out research on magnesium-based solid-state battery materials is of great significance to the sustainable development of future energy.
  • the embodiments of the present invention provide a magnesium-based solid electrolyte, a preparation method thereof, and a battery.
  • the preparation method combines multi-stage solid-phase low-temperature sintering with multiple crushings to prepare pure phase titanium magnesium phosphate powder. The reactivity between powder particles is enhanced, allowing secondary sintering to be performed at low temperatures.
  • the preparation method is highly safe and is conducive to the quantitative production of magnesium-based solid electrolyte titanium magnesium phosphate.
  • embodiments of the present invention provide a method for preparing a magnesium-based solid electrolyte.
  • the preparation method includes:
  • the sintered precursor is subjected to crushing treatment to obtain powder material;
  • the powder material is sintered at 900°C-1200°C for 5-10 hours in an air atmosphere, and the powder material is crystallized to obtain the magnesium-based solid electrolyte.
  • the specific steps of mixing the magnesium source compound, titanium source compound and phosphorus source compound according to the required stoichiometric ratio are:
  • the magnesium source compound, the titanium source compound and the phosphorus source compound are mixed according to a stoichiometric ratio of Mg:Ti:P of 1:5-9:7-15.
  • the magnesium source compound includes: one or more of magnesium oxide, magnesium carbonate, magnesium chloride, and magnesium hydroxide;
  • the titanium source compound includes: one or more of titanium oxide, titanium tetrachloride, and tetrabutyl titanate;
  • the phosphorus source compound includes: one or more of solid phosphoric acid powder, phosphorus pentoxide, ammonium dihydrogen phosphate, phosphorous acid, and hexametaphosphate.
  • the crushing treatment includes:
  • the sintered precursor is sequentially subjected to primary crushing through a jaw crusher and a roller crusher to obtain a first powder material with a particle size of 10 ⁇ m-20 ⁇ m;
  • the first powder material is ball milled at a ball milling frequency of 200 Hz and a ball milling time of 2 hours to obtain a second powder material with a particle size of 4 ⁇ m-15 ⁇ m;
  • the second powder material is subjected to jet milling treatment to obtain a powder material with a particle size of 2 ⁇ m-4 ⁇ m.
  • the method further includes:
  • the crystallized product is subjected to the crushing treatment to obtain the magnesium-based solid electrolyte.
  • embodiments of the present invention provide a magnesium-based solid electrolyte prepared by the method for preparing a magnesium-based solid electrolyte described in the first aspect.
  • the magnesium-based solid electrolyte is in the form of white powdery material with a particle size of 2 ⁇ m-4 ⁇ m.
  • the magnesium-based solid electrolyte is pure phase magnesium titanium phosphate, with a chemical formula of Mg 0.5 Ti 2 (PO 4 ) 3 .
  • the XRD diffraction peaks of the magnesium-based solid electrolyte correspond to the standard card number PDF#82-0297.
  • embodiments of the present invention provide a battery, which includes a magnesium-based solid electrolyte prepared by the method for preparing a magnesium-based solid electrolyte described in the first aspect.
  • the preparation method of the magnesium-based solid electrolyte proposed in the embodiment of the present invention prepares pure phase titanium magnesium phosphate powder through a combination of multi-stage solid-phase low-temperature sintering and multiple crushings.
  • the multiple crushings enhance the reactivity between powder particles. This enables secondary sintering to be carried out at low temperatures and the preparation method is safe. High, which is beneficial to the quantitative production of magnesium-based solid electrolyte titanium magnesium phosphate.
  • Figure 1 is a flow chart of a method for preparing a magnesium-based solid electrolyte according to an embodiment of the present invention
  • Figure 2 is an X-ray diffraction (XRD) pattern of the crushed sintered precursor in Example 1 of the present invention
  • Figure 3 is an X-ray diffraction (XRD) pattern of titanium magnesium phosphate prepared in Example 1 of the present invention.
  • the present invention proposes a method for preparing a magnesium-based solid electrolyte that can be used industrially, filling the gap in the industrial preparation of titanium magnesium phosphate solid electrolyte materials in the industry.
  • Step 110 Mix the magnesium source compound, titanium source compound and phosphorus source compound according to the required stoichiometric ratio to obtain a mixed precursor;
  • the magnesium source compound includes: one or more of magnesium oxide, magnesium carbonate, magnesium chloride, and magnesium hydroxide;
  • the titanium source compound includes: one or more of titanium oxide, titanium tetrachloride, and tetrabutyl titanate;
  • the phosphorus source compound includes: one or more of solid phosphoric acid powder, phosphorus pentoxide, ammonium dihydrogen phosphate, phosphorous acid, and hexametaphosphate.
  • the magnesium source compound, titanium source compound and phosphorus source compound are mixed according to a stoichiometric ratio of Mg:Ti:P in the selected compound of 1:5-9:7-15.
  • Step 120 Pre-sinter the mixed precursor in an air atmosphere at a sintering temperature of 500°C-700°C and a sintering time of 5-15 hours to obtain a sintered precursor;
  • Step 130 crush the sintered precursor to obtain powder material
  • the crushing treatment adopts a multiple crushing scheme, including:
  • Step 131 Pass the sintered precursor through the jaw crusher and the roller crusher for primary crushing in order to obtain the first powder material with a particle size of 10 ⁇ m-20 ⁇ m;
  • Step 132 Ball mill the first powder material with a ball milling frequency of 200 Hz and a ball milling time of 2 hours to obtain a second powder material with a particle size of 4 ⁇ m-15 ⁇ m;
  • Step 133 The second powder material is subjected to air flow milling to obtain a powder material with a particle size of 2 ⁇ m-4 ⁇ m.
  • the powder with large particle size obtained by jaw crushing and counter-roller crushing is further reduced in particle size through ball milling; finally, smaller, finer and uniform size powder is obtained through airflow milling. Powder.
  • the powder as fine and uniform as possible is obtained, thereby increasing the reactivity between secondary sintering powder particles.
  • Step 140 sinter the powder material at 900°C-1200°C for 5-10 hours in an air atmosphere, and perform crystallization treatment on the powder material to obtain a magnesium-based solid electrolyte.
  • the crystallized product is preferably subjected to crushing treatment.
  • the method can be the same as step 130, and finally a powdered magnesium-based solid electrolyte is obtained.
  • the magnesium-based solid electrolyte prepared by the present invention is pure phase magnesium titanium phosphate, with a chemical formula of Mg 0.5 Ti 2 (PO 4 ) 3 , in the form of white powder, and a particle size of 2 ⁇ m-4 ⁇ m.
  • the XRD diffraction peaks of the magnesium solid electrolyte correspond to the standard card number PDF#82-0297.
  • the magnesium-based solid electrolyte of the present invention can be used as a positive electrode material in magnesium ion batteries or solid-state batteries.
  • This embodiment proposes the preparation of a pure phase titanium magnesium phosphate solid electrolyte.
  • Step 1 Weigh the magnesium source compound magnesium oxide, the titanium source compound titanium oxide and the phosphorus source compound phosphorus pentoxide according to the stoichiometric ratio of Mg:Ti:P to 1:8:11. Weigh 51g of magnesium oxide, 406g of titanium oxide, and pentoxide. Pour 542g of diphosphorus oxide into the mixer MG20 and mix for 30 minutes to obtain a mixed precursor;
  • Step 2 Pre-sinter the mixed precursor.
  • the sintering equipment is a high-temperature box furnace RX3-50-14.
  • the sintering temperature is 600°C and the sintering time is 10 hours to obtain a sintered precursor.
  • Step 3 crush the sintered precursor obtained by sintering.
  • the sintered precursor is subjected to primary crushing through the jaw crusher DCI 150 ⁇ 200 and the roller crusher DCJ230 to obtain powder with a particle size Dv50 of 15.0 ⁇ m; then ball milling is performed in the ball milling equipment XQM-20.
  • the ball milling frequency is 200Hz and the ball milling time is 2 hours to obtain a powder with a particle size Dv50 of 8.2 ⁇ m.
  • air flow milling is performed to obtain a uniform powder material with a particle size Dv50 of 3.2 ⁇ m.
  • the sintered precursor after crushing was subjected to XRD scanning test using X-ray diffractometer equipment DX-2700B.
  • the results are shown in Figure 2.
  • About 90% of the diffraction peaks of the precursor material correspond to the standard peaks of titanium magnesium phosphate, but still There are miscellaneous peaks.
  • the existence of impurity peaks is due to the presence of other combinations of Mg/Ti/P/O elements besides magnesium titanium phosphate in the product.
  • the material is then crystallized, and the amorphous product is eliminated through secondary sintering to fully react, and pure phase titanium magnesium phosphate is obtained.
  • Step 4 Sinter the crushed sintered precursor material in a high-temperature box furnace RX3-50-14 equipment at 900°C for 5 hours to crystallize the material and cool it down to obtain a white hard block material, which is a pure phase of titanium magnesium phosphate.
  • step 3 crush the white hard block material in the same method as step 3 to obtain white powder with a particle size Dv50 of about 2 ⁇ m.
  • the powder was subjected to XRD scanning test.
  • the XRD results of the test are shown in Figure 3.
  • the diffraction peaks all correspond to the standard card PDF#82-0297. This result shows that pure phase titanium magnesium phosphate material was successfully prepared through multi-stage solid phase sintering process.
  • This embodiment proposes the preparation of a pure phase titanium magnesium phosphate solid electrolyte.
  • the equipment used in each step is the same as in Example 1.
  • Step 1 Weigh the magnesium source compound magnesium carbonate, the titanium source compound tetrabutyl titanate and the phosphorus source compound ammonium dihydrogen phosphate according to the stoichiometric ratio of Mg:Ti:P to 1:8:11. Pour butyl ester and ammonium dihydrogen phosphate into a mixer and mix for 30 minutes to obtain a mixed precursor;
  • Step 2 pre-sinter the mixed precursor at a sintering temperature of 700°C and a sintering time of 8 hours to obtain a sintered precursor.
  • Step 3 crush the sintered precursor obtained by sintering.
  • the sintered precursor is subjected to primary crushing through a jaw crusher and a roller crusher to obtain powder with a particle size of Dv50 of 14.6 ⁇ m; then ball milling is performed, with a ball milling frequency of 200Hz and a ball milling time of 2 hours. A powder with a particle size of Dv50 of 6.5 ⁇ m is obtained; finally, air flow milling is performed to obtain a uniform powder material with a particle size of Dv50 of 2.8 ⁇ m.
  • Step 4 sinter the crushed sintered precursor material at 900°C for 5 hours to crystallize the material, and then cool down to obtain a white hard block material, which is a pure phase of titanium magnesium phosphate.
  • step 3 crush the white hard block material in the same method as step 3 to obtain white powder with a particle size Dv50 of 2 ⁇ m.
  • the powder was subjected to XRD scanning testing, and the results showed that pure phase titanium magnesium phosphate material was successfully prepared through multi-stage solid phase sintering treatment.
  • This embodiment proposes the preparation of a titanium magnesium phosphate solid electrolyte.
  • the equipment used in each step is the same as in Example 1.
  • Step 1 Weigh the magnesium source compound magnesium chloride, the titanium source compound titanium tetrachloride and the phosphorus source compound phosphorous acid according to the stoichiometric ratio of Mg:Ti:P to 1:7:12. Put it into a mixer and mix for 30 minutes to obtain a mixed precursor;
  • Step 2 Pre-sinter the mixed precursor at a sintering temperature of 500°C and a sintering time of 10 hours, a sintering precursor is obtained.
  • Step 3 crush the sintered precursor obtained by sintering.
  • the sintered precursor is subjected to primary crushing through a jaw crusher and a roller crusher to obtain powder with a particle size Dv50 of 16.1 ⁇ m; then ball milling is performed, with a ball milling frequency of 200Hz and a ball milling time of 2 hours, to obtain The powder with a particle size Dv50 of 7.3 ⁇ m is finally subjected to air flow milling to obtain a uniform powder material with a particle size Dv50 of 2.5 ⁇ m.
  • Step 4 sinter the crushed sintered precursor material at 900°C for 5 hours to crystallize the material, and then cool down to obtain a white hard block material, which is a pure phase of titanium magnesium phosphate.
  • step 3 crush the white hard block material in the same method as step 3 to obtain white powder with a particle size Dv50 of about 2 ⁇ m.
  • the preparation method of the magnesium-based solid electrolyte proposed in the embodiment of the present invention prepares pure phase titanium magnesium phosphate powder through a combination of multi-stage solid-phase low-temperature sintering and multiple crushings.
  • the multiple crushings enhance the reactivity between powder particles.
  • the secondary sintering can be carried out at low temperature, the preparation method is highly safe, the raw materials used are cheap, the production cost is reduced, and it is conducive to the quantitative production of magnesium-based solid electrolyte titanium magnesium phosphate.
  • the invention improves the application of magnesium-based materials in solid-state batteries and alleviates the resource shortage problem caused by lithium raw materials, and is of great significance to the sustainable development of future energy.

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Abstract

The present invention relates to a magnesium-based solid electrolyte, a preparation method therefor, and a battery. The preparation method comprises: mixing a magnesium source compound, a titanium source compound and a phosphorus source compound according to a required stoichiometric ratio to obtain a mixed precursor; pre-sintering the mixed precursor in an air atmosphere at a temperature of 500-700°C for 5-15 h to obtain a sintered precursor; crushing the sintered precursor to obtain a powder material; and sintering the powder material in an air atmosphere at 900-1200°C for 5-10 h, and subjecting the powder material to crystallization treatment so as to obtain a magnesium-based solid electrolyte.

Description

一种镁系固态电解质及其制备方法和电池A kind of magnesium-based solid electrolyte and its preparation method and battery
本申请要求于2022年07月27日提交中国专利局、申请号为202210891794.X、发明名称为“一种镁系固态电解质及其制备方法和电池”的中国专利申请的优先权。This application claims priority to the Chinese patent application submitted to the China Patent Office on July 27, 2022, with the application number 202210891794.X and the invention title "A magnesium-based solid electrolyte and its preparation method and battery".
技术领域Technical field
本发明涉及新能源电池材料技术领域，尤其涉及一种镁系固态电解质及其制备方法和电池。The present invention relates to the technical field of new energy battery materials, and in particular to a magnesium-based solid electrolyte and its preparation method and battery.
背景技术Background technique
全球环境的不断恶化和能源供应的持续紧缺是21世纪人类必须面临的最严重的两大问题,开发应用新能源和可再生清洁能源已经刻不容缓；锂离子二次电池作为新型的绿色电池,自从1990年问世以来发展相当迅速。The continuous deterioration of the global environment and the continued shortage of energy supply are the two most serious problems that humans must face in the 21st century. The development and application of new energy and renewable clean energy has become urgent; lithium-ion secondary batteries, as a new type of green battery, have been around since 1990. It has developed rapidly since its inception.
随着锂离子电池的巨大成功，同样地，在元素周期表上与锂处于对角线位置的镁；其离子半径、化学性质与锂相似，此外，镁作为地球上储量最丰富的轻金属元素之一，被广泛应用于各个领域。由此种种，对镁元素在固态电解质领域的研究引起越来越多的科研人员的关注。如中国专利202010803639.9公开了一种可充镁电池正极材料及其制备方法。可充镁电池正极材料包括的黄铁矿型化合物能够同时实现阳离子和阴离子的氧化还原变价，提高正极材料的容量和电压。With the great success of lithium-ion batteries, magnesium, which is diagonal to lithium on the periodic table, has similar ionic radius and chemical properties to lithium. In addition, magnesium is one of the most abundant light metal elements on the earth. 1. It is widely used in various fields. For this reason, the study of magnesium in the field of solid electrolytes has attracted the attention of more and more scientific researchers. For example, Chinese patent 202010803639.9 discloses a rechargeable magnesium battery cathode material and its preparation method. The pyrite-type compound included in the cathode material of the rechargeable magnesium battery can realize the redox and price conversion of cations and anions at the same time, thereby increasing the capacity and voltage of the cathode material.
此外，镁不如锂活泼，易操作；无污染，安全性好。价格低廉，其价格仅为锂的1/24。因此，开展镁系材料在固态电解质中的研究，一方面可以缓解锂原料紧缺带来的经济问题；另一方面开展镁系固态电池材料的相关研究工作对未来能源的可持续发展具有重要意义。 In addition, magnesium is not as active as lithium and is easy to operate; it is pollution-free and has good safety. Low price, its price is only 1/24 of lithium. Therefore, carrying out research on magnesium-based materials in solid-state electrolytes can, on the one hand, alleviate the economic problems caused by the shortage of lithium raw materials; on the other hand, carrying out research on magnesium-based solid-state battery materials is of great significance to the sustainable development of future energy.
然而，基于目前公开报道中，关于磷酸钛镁材料制备方法，尤其是适合于工业化量产的制备方法，还未见公开。However, based on the current public reports, there is no disclosure about the preparation method of titanium magnesium phosphate material, especially the preparation method suitable for industrial mass production.
发明内容Contents of the invention
本发明实施例提供了一种镁系固态电解质及其制备方法和电池，该制备方法通过多阶段固相低温烧结与多次破碎相结合，制备得到纯相磷酸钛镁粉体，通过多次破碎增强了粉体颗粒间的反应活性，使得二次烧结能够在低温下进行，制备方法安全性高，利于镁系固态电解质磷酸钛镁的量化生产。The embodiments of the present invention provide a magnesium-based solid electrolyte, a preparation method thereof, and a battery. The preparation method combines multi-stage solid-phase low-temperature sintering with multiple crushings to prepare pure phase titanium magnesium phosphate powder. The reactivity between powder particles is enhanced, allowing secondary sintering to be performed at low temperatures. The preparation method is highly safe and is conducive to the quantitative production of magnesium-based solid electrolyte titanium magnesium phosphate.
第一方面，本发明实施例提供了一种镁系固态电解质的制备方法，所述制备方法包括：In a first aspect, embodiments of the present invention provide a method for preparing a magnesium-based solid electrolyte. The preparation method includes:
将镁源化合物、钛源化合物和磷源化合物按照所需化学计量比混合，得到混合前驱体；Mix the magnesium source compound, titanium source compound and phosphorus source compound according to the required stoichiometric ratio to obtain a mixed precursor;
将所述混合前驱体在空气气氛中进行预烧，烧结温度为500℃-700℃，烧结时间为5-15小时，得到烧结前驱体；Pre-sinter the mixed precursor in an air atmosphere at a sintering temperature of 500°C-700°C and a sintering time of 5-15 hours to obtain a sintered precursor;
将所述烧结前驱体进行破碎处理，得到粉体材料；The sintered precursor is subjected to crushing treatment to obtain powder material;
将所述粉体材料在空气气氛中900℃-1200℃烧结5-10小时，对所述粉体材料进行晶化处理，得到所述镁系固态电解质。The powder material is sintered at 900°C-1200°C for 5-10 hours in an air atmosphere, and the powder material is crystallized to obtain the magnesium-based solid electrolyte.
优选的，，所述将镁源化合物、钛源化合物和磷源化合物按照所需化学计量比混合具体为：Preferably, the specific steps of mixing the magnesium source compound, titanium source compound and phosphorus source compound according to the required stoichiometric ratio are:
按照化学计量比Mg:Ti:P为1：5-9：7-15的比例混合镁源化合物、钛源化合物和磷源化合物。The magnesium source compound, the titanium source compound and the phosphorus source compound are mixed according to a stoichiometric ratio of Mg:Ti:P of 1:5-9:7-15.
优选的，所述镁源化合物包括：氧化镁、碳酸镁、氯化镁、氢氧化镁中的一种或多种；Preferably, the magnesium source compound includes: one or more of magnesium oxide, magnesium carbonate, magnesium chloride, and magnesium hydroxide;
所述钛源化合物包括：氧化钛、四氯化钛、钛酸四丁酯中的一种或多种； The titanium source compound includes: one or more of titanium oxide, titanium tetrachloride, and tetrabutyl titanate;
所述磷源化合物包括：固态磷酸粉末、五氧化二磷、磷酸二氢铵、亚磷酸、六偏磷酸盐中的一种或多种。The phosphorus source compound includes: one or more of solid phosphoric acid powder, phosphorus pentoxide, ammonium dihydrogen phosphate, phosphorous acid, and hexametaphosphate.
优选的，所述破碎处理包括：Preferably, the crushing treatment includes:
将所述烧结前驱体依次通过颚式破碎机和对辊破碎机进行初级破碎，得到粒径大小为10μm-20μm的第一粉体物料；The sintered precursor is sequentially subjected to primary crushing through a jaw crusher and a roller crusher to obtain a first powder material with a particle size of 10 μm-20 μm;
将所述第一粉体物料进行球磨处理，球磨频率为200Hz，球磨时间为2小时，得到粒径大小为4μm-15μm的第二粉体物料；The first powder material is ball milled at a ball milling frequency of 200 Hz and a ball milling time of 2 hours to obtain a second powder material with a particle size of 4 μm-15 μm;
将所述第二粉体物料进行气流磨处理，得到粒径大小为2μm-4μm的粉体材料。The second powder material is subjected to jet milling treatment to obtain a powder material with a particle size of 2 μm-4 μm.
进一步优选的，在对所述粉体材料进行晶化处理之后，所述方法还包括：Further preferably, after crystallizing the powder material, the method further includes:
对所述晶化处理后的产物进行所述破碎处理，得到所述镁系固态电解质。The crystallized product is subjected to the crushing treatment to obtain the magnesium-based solid electrolyte.
第二方面，本发明实施例提供了一种第一方面所述的镁系固态电解质的制备方法制备得到的镁系固态电解质。In a second aspect, embodiments of the present invention provide a magnesium-based solid electrolyte prepared by the method for preparing a magnesium-based solid electrolyte described in the first aspect.
优选的，所述镁系固态电解质呈白色粉末状物料，粒径大小为2μm-4μm。Preferably, the magnesium-based solid electrolyte is in the form of white powdery material with a particle size of 2 μm-4 μm.
优选的，所述镁系固态电解质为纯相磷酸钛镁，化学式为Mg0.5Ti2(PO4)3。Preferably, the magnesium-based solid electrolyte is pure phase magnesium titanium phosphate, with a chemical formula of Mg 0.5 Ti 2 (PO 4 ) 3 .
优选的，所述镁系固态电解质的XRD衍射峰与标准卡片卡号为PDF#82-0297一一对应。Preferably, the XRD diffraction peaks of the magnesium-based solid electrolyte correspond to the standard card number PDF#82-0297.
第三方面，本发明实施例提供了一种电池，所述电池包括第一方面所述的镁系固态电解质的制备方法制备得到的镁系固态电解质。In a third aspect, embodiments of the present invention provide a battery, which includes a magnesium-based solid electrolyte prepared by the method for preparing a magnesium-based solid electrolyte described in the first aspect.
本发明实施例提出的镁系固态电解质的制备方法，通过多阶段固相低温烧结与多次破碎相结合制备纯相磷酸钛镁粉体，通过多次破碎增强了粉体颗粒间的反应活性，使得二次烧结能够在低温下进行，制备方法安全性 高，有利于镁系固态电解质磷酸钛镁的量化生产。The preparation method of the magnesium-based solid electrolyte proposed in the embodiment of the present invention prepares pure phase titanium magnesium phosphate powder through a combination of multi-stage solid-phase low-temperature sintering and multiple crushings. The multiple crushings enhance the reactivity between powder particles. This enables secondary sintering to be carried out at low temperatures and the preparation method is safe. High, which is beneficial to the quantitative production of magnesium-based solid electrolyte titanium magnesium phosphate.
附图说明Description of drawings
下面通过附图和实施例，对本发明实施例的技术方案做进一步详细描述。The technical solutions of the embodiments of the present invention will be described in further detail below through the accompanying drawings and examples.
图1为本发明实施例的镁系固态电解质的制备方法流程图；Figure 1 is a flow chart of a method for preparing a magnesium-based solid electrolyte according to an embodiment of the present invention;
图2为本发明实施例1中破碎后的烧结前驱体的X射线衍射(XRD)图；Figure 2 is an X-ray diffraction (XRD) pattern of the crushed sintered precursor in Example 1 of the present invention;
图3是本发明实施例1制备得到的磷酸钛镁的X射线衍射(XRD)图。Figure 3 is an X-ray diffraction (XRD) pattern of titanium magnesium phosphate prepared in Example 1 of the present invention.
具体实施方式Detailed ways
下面通过附图和具体的实施例，对本发明进行进一步的说明，但应当理解为这些实施例仅仅是用于更详细说明之用，而不应理解为用以任何形式限制本发明，即并不意于限制本发明的保护范围。The present invention will be further described below through the drawings and specific examples. However, it should be understood that these examples are only for more detailed description and should not be understood as limiting the present invention in any form, that is, they are not intended to limit the present invention. To limit the scope of protection of the present invention.
本发明提出了一种能够产业化应用的镁系固态电解质的制备方法，填补了业内磷酸钛镁固态电解质材料的产业化制备的空白。The present invention proposes a method for preparing a magnesium-based solid electrolyte that can be used industrially, filling the gap in the industrial preparation of titanium magnesium phosphate solid electrolyte materials in the industry.
本发明的主要制备步骤如图1所示，包括：The main preparation steps of the present invention are shown in Figure 1, including:
步骤110，将镁源化合物、钛源化合物和磷源化合物按照所需化学计量比混合，得到混合前驱体；Step 110: Mix the magnesium source compound, titanium source compound and phosphorus source compound according to the required stoichiometric ratio to obtain a mixed precursor;
镁源化合物包括：氧化镁、碳酸镁、氯化镁、氢氧化镁中的一种或多种；钛源化合物包括：氧化钛、四氯化钛、钛酸四丁酯中的一种或多种；磷源化合物包括：固态磷酸粉末、五氧化二磷、磷酸二氢铵、亚磷酸、六偏磷酸盐中的一种或多种。The magnesium source compound includes: one or more of magnesium oxide, magnesium carbonate, magnesium chloride, and magnesium hydroxide; the titanium source compound includes: one or more of titanium oxide, titanium tetrachloride, and tetrabutyl titanate; The phosphorus source compound includes: one or more of solid phosphoric acid powder, phosphorus pentoxide, ammonium dihydrogen phosphate, phosphorous acid, and hexametaphosphate.
镁源化合物、钛源化合物和磷源化合物按照所选化合物中Mg:Ti:P的化学计量比为1：5-9：7-15的比例进行混合。The magnesium source compound, titanium source compound and phosphorus source compound are mixed according to a stoichiometric ratio of Mg:Ti:P in the selected compound of 1:5-9:7-15.
步骤120，将混合前驱体在空气气氛中进行预烧，烧结温度为500℃-700℃，烧结时间为5-15小时，得到烧结前驱体； Step 120: Pre-sinter the mixed precursor in an air atmosphere at a sintering temperature of 500°C-700°C and a sintering time of 5-15 hours to obtain a sintered precursor;
步骤130，将烧结前驱体进行破碎处理，得到粉体材料；Step 130: crush the sintered precursor to obtain powder material;
在本发明中，破碎处理采用多次破碎的方案，包括：In the present invention, the crushing treatment adopts a multiple crushing scheme, including:
步骤131，将烧结前驱体依次通过颚式破碎机和对辊破碎机进行初级破碎，得到粒径大小为10μm-20μm的第一粉体物料；Step 131: Pass the sintered precursor through the jaw crusher and the roller crusher for primary crushing in order to obtain the first powder material with a particle size of 10 μm-20 μm;
步骤132，将第一粉体物料进行球磨处理，球磨频率为200Hz，球磨时间为2小时，得到粒径大小为4μm-15μm的第二粉体物料；Step 132: Ball mill the first powder material with a ball milling frequency of 200 Hz and a ball milling time of 2 hours to obtain a second powder material with a particle size of 4 μm-15 μm;
步骤133，将第二粉体物料进行气流磨处理，得到粒径大小为2μm-4μm的粉体材料。Step 133: The second powder material is subjected to air flow milling to obtain a powder material with a particle size of 2 μm-4 μm.
本发明的分布多次破碎过程中，鄂破和对辊破碎得到的粒径大的粉体，通过球磨处理使得粉体粒径进一步减小；最终通过气流磨得到更小更细且大小均一的粉体。通过上述多级破碎过程得到尽可能细且均匀的粉体，从而增加二次烧结粉体颗粒间的反应活性。In the distributed multiple crushing process of the present invention, the powder with large particle size obtained by jaw crushing and counter-roller crushing is further reduced in particle size through ball milling; finally, smaller, finer and uniform size powder is obtained through airflow milling. Powder. Through the above-mentioned multi-stage crushing process, the powder as fine and uniform as possible is obtained, thereby increasing the reactivity between secondary sintering powder particles.
步骤140，将粉体材料在空气气氛中900℃-1200℃烧结5-10小时，对粉体材料进行晶化处理，得到镁系固态电解质。Step 140: sinter the powder material at 900°C-1200°C for 5-10 hours in an air atmosphere, and perform crystallization treatment on the powder material to obtain a magnesium-based solid electrolyte.
进一步的，在进行晶化处理之后，优选的，还要对晶化处理后的产物再进行破碎处理，方法可同步骤130，最终得到粉末状的镁系固态电解质。Further, after the crystallization treatment is performed, the crystallized product is preferably subjected to crushing treatment. The method can be the same as step 130, and finally a powdered magnesium-based solid electrolyte is obtained.
本发明制备所得的镁系固态电解质为纯相的磷酸钛镁，化学式为Mg0.5Ti2(PO4)3，呈白色粉末状，粒径大小为2μm-4μm。镁系固态电解质的XRD衍射峰与标准卡片卡号为PDF#82-0297一一对应。The magnesium-based solid electrolyte prepared by the present invention is pure phase magnesium titanium phosphate, with a chemical formula of Mg 0.5 Ti 2 (PO 4 ) 3 , in the form of white powder, and a particle size of 2 μm-4 μm. The XRD diffraction peaks of the magnesium solid electrolyte correspond to the standard card number PDF#82-0297.
本发明的镁系固态电解质可作为正极材料应用在镁离子电池或固态电池中。The magnesium-based solid electrolyte of the present invention can be used as a positive electrode material in magnesium ion batteries or solid-state batteries.
为更好的理解本发明提供的技术方案，下述以一些具体实例分别说明应用本发明上述实施例提供的方法制备镁系固态电解质的具体过程以及特性。In order to better understand the technical solutions provided by the present invention, the specific process and characteristics of preparing magnesium-based solid electrolytes using the methods provided by the above embodiments of the present invention are described below with some specific examples.
实施例1 Example 1
本实施例提出一种纯相磷酸钛镁固态电解质的制备。This embodiment proposes the preparation of a pure phase titanium magnesium phosphate solid electrolyte.
步骤1，将镁源化合物氧化镁，钛源化合物氧化钛和磷源化合物五氧化二磷按照Mg:Ti:P的化学计量比为1：8：11称取氧化镁51g、氧化钛406g、五氧化二磷542g倒入混料机MG20中混合30分钟，得到混合前驱体；Step 1: Weigh the magnesium source compound magnesium oxide, the titanium source compound titanium oxide and the phosphorus source compound phosphorus pentoxide according to the stoichiometric ratio of Mg:Ti:P to 1:8:11. Weigh 51g of magnesium oxide, 406g of titanium oxide, and pentoxide. Pour 542g of diphosphorus oxide into the mixer MG20 and mix for 30 minutes to obtain a mixed precursor;
步骤2，将混合前驱体进行预烧，烧结设备为高温箱式炉RX3-50-14，烧结温度为600℃，烧结时间为10小时，得到烧结前驱体。Step 2: Pre-sinter the mixed precursor. The sintering equipment is a high-temperature box furnace RX3-50-14. The sintering temperature is 600°C and the sintering time is 10 hours to obtain a sintered precursor.
步骤3，将烧结得到的烧结前驱体进行破碎处理。Step 3: crush the sintered precursor obtained by sintering.
首先，将烧结前驱体先后通过颚式破碎机DCI 150×200和对辊破碎机DCJ230进行初级破碎，得到粒径大小Dv50为15.0μm的粉体；然后在球磨设备XQM-20中进行球磨处理，球磨频率为200Hz，球磨时间为2小时，得到粒径大小Dv50为8.2μm的粉体；最后再进行气流磨处理，得到粒径大小Dv50为3.2μm的均匀粉体材料。First, the sintered precursor is subjected to primary crushing through the jaw crusher DCI 150×200 and the roller crusher DCJ230 to obtain powder with a particle size Dv50 of 15.0 μm; then ball milling is performed in the ball milling equipment XQM-20. The ball milling frequency is 200Hz and the ball milling time is 2 hours to obtain a powder with a particle size Dv50 of 8.2 μm. Finally, air flow milling is performed to obtain a uniform powder material with a particle size Dv50 of 3.2 μm.
经过破碎处理后的烧结前驱体通过X射线衍射仪设备DX-2700B进行XRD扫描测试，结果如图2所示，该前驱体材料约90％的衍射峰与磷酸钛镁的标准峰对应，但还是存在杂峰。杂峰的存在是因为产物中存在磷酸钛镁之外Mg/Ti/P/O元素的其它组合物。为得到纯相的磷酸钛镁材料，再对材料进行晶化处理，通过二次烧结充分反应消除非晶化产物，得到纯相的磷酸钛镁。The sintered precursor after crushing was subjected to XRD scanning test using X-ray diffractometer equipment DX-2700B. The results are shown in Figure 2. About 90% of the diffraction peaks of the precursor material correspond to the standard peaks of titanium magnesium phosphate, but still There are miscellaneous peaks. The existence of impurity peaks is due to the presence of other combinations of Mg/Ti/P/O elements besides magnesium titanium phosphate in the product. In order to obtain pure phase titanium magnesium phosphate material, the material is then crystallized, and the amorphous product is eliminated through secondary sintering to fully react, and pure phase titanium magnesium phosphate is obtained.
步骤4，将破碎后的烧结前驱体材料在高温箱式炉RX3-50-14设备中900℃烧结5小时，使材料晶化，降温得到白色坚硬块状物料，为纯相的磷酸钛镁。Step 4: Sinter the crushed sintered precursor material in a high-temperature box furnace RX3-50-14 equipment at 900°C for 5 hours to crystallize the material and cool it down to obtain a white hard block material, which is a pure phase of titanium magnesium phosphate.
进一步的，对白色坚硬块状物料再执行步骤3相同方法的破碎，从而得到粒径大小Dv50为2μm左右的白色粉体。将该粉体进行XRD扫描测试。测试得XRD结果如图3所示，衍射峰均与标准卡片PDF#82-0297一一对应。该结果表明，通过多阶段固相烧结处理成功制备出纯相的磷酸钛镁材料。 Further, crush the white hard block material in the same method as step 3 to obtain white powder with a particle size Dv50 of about 2 μm. The powder was subjected to XRD scanning test. The XRD results of the test are shown in Figure 3. The diffraction peaks all correspond to the standard card PDF#82-0297. This result shows that pure phase titanium magnesium phosphate material was successfully prepared through multi-stage solid phase sintering process.
实施例2Example 2
本实施例提出一种纯相磷酸钛镁固态电解质的制备。各步骤所用设备与实施例1相同。This embodiment proposes the preparation of a pure phase titanium magnesium phosphate solid electrolyte. The equipment used in each step is the same as in Example 1.
步骤1，将镁源化合物碳酸镁，钛源化合物钛酸四丁酯和磷源化合物磷酸二氢铵按照Mg:Ti:P的化学计量比为1：8：11称取碳酸镁、钛酸四丁酯、磷酸二氢铵倒入混料机中混合30分钟，得到混合前驱体；Step 1: Weigh the magnesium source compound magnesium carbonate, the titanium source compound tetrabutyl titanate and the phosphorus source compound ammonium dihydrogen phosphate according to the stoichiometric ratio of Mg:Ti:P to 1:8:11. Pour butyl ester and ammonium dihydrogen phosphate into a mixer and mix for 30 minutes to obtain a mixed precursor;
步骤2，将混合前驱体进行预烧，烧结温度为700℃，烧结时间为8小时，得到烧结前驱体。Step 2: pre-sinter the mixed precursor at a sintering temperature of 700°C and a sintering time of 8 hours to obtain a sintered precursor.
步骤3，将烧结得到的烧结前驱体进行破碎处理。Step 3: crush the sintered precursor obtained by sintering.
首先，将烧结前驱体先后通过颚式破碎机和对辊破碎机进行初级破碎，得到粒径大小为Dv50为14.6μm的粉体；然后进行球磨处理，球磨频率为200Hz，球磨时间为2小时，得到粒径大小为Dv50为6.5μm的粉体；最后再进行气流磨处理，得到粒径大小为Dv50为2.8μm的均匀粉体材料。First, the sintered precursor is subjected to primary crushing through a jaw crusher and a roller crusher to obtain powder with a particle size of Dv50 of 14.6 μm; then ball milling is performed, with a ball milling frequency of 200Hz and a ball milling time of 2 hours. A powder with a particle size of Dv50 of 6.5 μm is obtained; finally, air flow milling is performed to obtain a uniform powder material with a particle size of Dv50 of 2.8 μm.
步骤4，将破碎后的烧结前驱体材料在900℃烧结5小时，使材料晶化，降温得到白色坚硬块状物料，为纯相的磷酸钛镁。Step 4: sinter the crushed sintered precursor material at 900°C for 5 hours to crystallize the material, and then cool down to obtain a white hard block material, which is a pure phase of titanium magnesium phosphate.
进一步的，对白色坚硬块状物料再执行步骤3相同方法的破碎，从而得到粒径大小Dv50为2μm的白色粉体。将该粉体进行XRD扫描测试，结果表明，通过多阶段固相烧结处理成功制备出纯相的磷酸钛镁材料。Further, crush the white hard block material in the same method as step 3 to obtain white powder with a particle size Dv50 of 2 μm. The powder was subjected to XRD scanning testing, and the results showed that pure phase titanium magnesium phosphate material was successfully prepared through multi-stage solid phase sintering treatment.
实施例3Example 3
本实施例提出一种磷酸钛镁固态电解质的制备。各步骤所用设备与实施例1相同。This embodiment proposes the preparation of a titanium magnesium phosphate solid electrolyte. The equipment used in each step is the same as in Example 1.
步骤1，将镁源化合物氯化镁，钛源化合物四氯化钛和磷源化合物亚磷酸按照Mg:Ti:P的化学计量比为1：7：12称取氯化镁、四氯化钛、亚磷酸倒入混料机中混合30分钟，得到混合前驱体；Step 1: Weigh the magnesium source compound magnesium chloride, the titanium source compound titanium tetrachloride and the phosphorus source compound phosphorous acid according to the stoichiometric ratio of Mg:Ti:P to 1:7:12. Put it into a mixer and mix for 30 minutes to obtain a mixed precursor;
步骤2，将混合前驱体进行预烧，烧结温度为500℃，烧结时间为10 小时，得到烧结前驱体。Step 2: Pre-sinter the mixed precursor at a sintering temperature of 500°C and a sintering time of 10 hours, a sintering precursor is obtained.
步骤3，将烧结得到的烧结前驱体进行破碎处理。Step 3: crush the sintered precursor obtained by sintering.
首先，将烧结前驱体先后通过颚式破碎机和对辊破碎机进行初级破碎，得到粒径大小Dv50为16.1μm的粉体；然后进行球磨处理，球磨频率为200Hz，球磨时间为2小时，得到粒径大小Dv50为7.3μm的粉体；最后再进行气流磨处理，得到粒径大小Dv50为2.5μm的均匀粉体材料。First, the sintered precursor is subjected to primary crushing through a jaw crusher and a roller crusher to obtain powder with a particle size Dv50 of 16.1 μm; then ball milling is performed, with a ball milling frequency of 200Hz and a ball milling time of 2 hours, to obtain The powder with a particle size Dv50 of 7.3 μm is finally subjected to air flow milling to obtain a uniform powder material with a particle size Dv50 of 2.5 μm.
步骤4，将破碎后的烧结前驱体材料在900℃烧结5小时，使材料晶化，降温得到白色坚硬块状物料，为纯相的磷酸钛镁。Step 4: sinter the crushed sintered precursor material at 900°C for 5 hours to crystallize the material, and then cool down to obtain a white hard block material, which is a pure phase of titanium magnesium phosphate.
进一步的，对白色坚硬块状物料再执行步骤3相同方法的破碎，从而得到粒径大小Dv50为2μm左右的白色粉体。Further, crush the white hard block material in the same method as step 3 to obtain white powder with a particle size Dv50 of about 2 μm.
本发明实施例提出的镁系固态电解质的制备方法，通过多阶段固相低温烧结与多次破碎相结合制备纯相磷酸钛镁粉体，通过多次破碎增强了粉体颗粒间的反应活性，使得二次烧结能够在低温下进行，制备方法安全性高，所用原料便宜，减少生产成本，有利于镁系固态电解质磷酸钛镁的量化生产。本发明提高了镁系材料在固态电池中的应用和减缓锂原料带来的资源紧缺问题，对未来能源的可持续发展具有重要意义。The preparation method of the magnesium-based solid electrolyte proposed in the embodiment of the present invention prepares pure phase titanium magnesium phosphate powder through a combination of multi-stage solid-phase low-temperature sintering and multiple crushings. The multiple crushings enhance the reactivity between powder particles. The secondary sintering can be carried out at low temperature, the preparation method is highly safe, the raw materials used are cheap, the production cost is reduced, and it is conducive to the quantitative production of magnesium-based solid electrolyte titanium magnesium phosphate. The invention improves the application of magnesium-based materials in solid-state batteries and alleviates the resource shortage problem caused by lithium raw materials, and is of great significance to the sustainable development of future energy.
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The above-mentioned specific embodiments further describe the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above-mentioned are only specific embodiments of the present invention and are not intended to limit the scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims (10)

  1. 一种镁系固态电解质的制备方法，其特征在于，所述制备方法包括：A method for preparing a magnesium-based solid electrolyte, characterized in that the preparation method includes:
    将镁源化合物、钛源化合物和磷源化合物按照所需化学计量比混合，得到混合前驱体；Mix the magnesium source compound, titanium source compound and phosphorus source compound according to the required stoichiometric ratio to obtain a mixed precursor;
    将所述混合前驱体在空气气氛中进行预烧，烧结温度为500℃-700℃，烧结时间为5-15小时，得到烧结前驱体；Pre-sinter the mixed precursor in an air atmosphere at a sintering temperature of 500°C-700°C and a sintering time of 5-15 hours to obtain a sintered precursor;
    将所述烧结前驱体进行破碎处理，得到粉体材料；The sintered precursor is subjected to crushing treatment to obtain powder material;
    将所述粉体材料在空气气氛中900℃-1200℃烧结5-10小时，对所述粉体材料进行晶化处理，得到所述镁系固态电解质。The powder material is sintered at 900°C-1200°C for 5-10 hours in an air atmosphere, and the powder material is crystallized to obtain the magnesium-based solid electrolyte.
  2. 根据权利要求1所述的制备方法，其特征在于，所述将镁源化合物、钛源化合物和磷源化合物按照所需化学计量比混合具体为：The preparation method according to claim 1, wherein the mixing of the magnesium source compound, the titanium source compound and the phosphorus source compound according to the required stoichiometric ratio is specifically:
    按照化学计量比Mg:Ti:P为1：5-9：7-15的比例混合镁源化合物、钛源化合物和磷源化合物。The magnesium source compound, the titanium source compound and the phosphorus source compound are mixed according to a stoichiometric ratio of Mg:Ti:P of 1:5-9:7-15.
  3. 根据权利要求1所述的制备方法，其特征在于，The preparation method according to claim 1, characterized in that:
    所述镁源化合物包括：氧化镁、碳酸镁、氯化镁、氢氧化镁中的一种或多种；The magnesium source compound includes: one or more of magnesium oxide, magnesium carbonate, magnesium chloride, and magnesium hydroxide;
    所述钛源化合物包括：氧化钛、四氯化钛、钛酸四丁酯中的一种或多种；The titanium source compound includes: one or more of titanium oxide, titanium tetrachloride, and tetrabutyl titanate;
    所述磷源化合物包括：固态磷酸粉末、五氧化二磷、磷酸二氢铵、亚磷酸、六偏磷酸盐中的一种或多种。The phosphorus source compound includes: one or more of solid phosphoric acid powder, phosphorus pentoxide, ammonium dihydrogen phosphate, phosphorous acid, and hexametaphosphate.
  4. 根据权利要求1所述的制备方法，其特征在于，所述破碎处理包括：The preparation method according to claim 1, characterized in that the crushing treatment includes:
    将所述烧结前驱体依次通过颚式破碎机和对辊破碎机进行初级破碎，得到粒径大小为10μm-20μm的第一粉体物料；The sintered precursor is sequentially subjected to primary crushing through a jaw crusher and a roller crusher to obtain a first powder material with a particle size of 10 μm-20 μm;
    将所述第一粉体物料进行球磨处理，球磨频率为200Hz，球磨时间为2小时，得到粒径大小为4μm-15μm的第二粉体物料；The first powder material is ball milled at a ball milling frequency of 200 Hz and a ball milling time of 2 hours to obtain a second powder material with a particle size of 4 μm-15 μm;
    将所述第二粉体物料进行气流磨处理，得到粒径大小为2μm-4μm的 粉体材料。The second powder material is subjected to jet milling treatment to obtain a particle size of 2 μm-4 μm. Powder materials.
  5. 根据权利要求4所述的制备方法，其特征在于，在对所述粉体材料进行晶化处理之后，所述方法还包括：The preparation method according to claim 4, characterized in that, after crystallizing the powder material, the method further includes:
    对所述晶化处理后的产物进行所述破碎处理，得到所述镁系固态电解质。The crystallized product is subjected to the crushing treatment to obtain the magnesium-based solid electrolyte.
  6. 一种上述权利要求1-5任一所述的镁系固态电解质的制备方法制备得到的镁系固态电解质。A magnesium-based solid electrolyte prepared by the method for preparing a magnesium-based solid electrolyte according to any one of claims 1 to 5.
  7. 根据权利要求6所述的镁系固态电解质，其特征在于，所述镁系固态电解质呈白色粉末状物料，粒径大小为2μm-4μm。The magnesium-based solid electrolyte according to claim 6, characterized in that the magnesium-based solid electrolyte is in the form of white powdery material with a particle size of 2 μm-4 μm.
  8. 根据权利要求6所述的镁系固态电解质，其特征在于，所述镁系固态电解质为纯相磷酸钛镁，化学式为Mg0.5Ti2(PO4)3。The magnesium-based solid electrolyte according to claim 6, characterized in that the magnesium-based solid electrolyte is pure phase magnesium titanium phosphate, with a chemical formula of Mg 0.5 Ti 2 (PO 4 ) 3 .
  9. 根据权利要求6所述的镁系固态电解质，其特征在于，所述镁系固态电解质的XRD衍射峰与标准卡片卡号为PDF#82-0297一一对应。The magnesium-based solid electrolyte according to claim 6, wherein the XRD diffraction peak of the magnesium-based solid electrolyte corresponds to a standard card number PDF#82-0297.
  10. 一种电池，其特征在于，所述电池包括上述权利要求1-5所述的镁系固态电解质的制备方法制备得到的镁系固态电解质。 A battery, characterized in that the battery includes a magnesium-based solid electrolyte prepared by the method for preparing a magnesium-based solid electrolyte according to claims 1-5.
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