WO2025213595A1 - 一种氧卤化物及其制备方法与全固态锂电池 - Google Patents

一种氧卤化物及其制备方法与全固态锂电池

Info

Publication number
WO2025213595A1
WO2025213595A1 PCT/CN2024/104098 CN2024104098W WO2025213595A1 WO 2025213595 A1 WO2025213595 A1 WO 2025213595A1 CN 2024104098 W CN2024104098 W CN 2024104098W WO 2025213595 A1 WO2025213595 A1 WO 2025213595A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
oxyhalide
calcination
solid
source
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/104098
Other languages
English (en)
French (fr)
Inventor
黄富强
曹宇舸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jiao Tong University
Original Assignee
Shanghai Jiao Tong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Jiao Tong University filed Critical Shanghai Jiao Tong University
Priority to KR1020247031874A priority Critical patent/KR102816302B1/ko
Publication of WO2025213595A1 publication Critical patent/WO2025213595A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C01B35/00—Boron; Compounds thereof
    • C01B35/06—Boron halogen compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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

Definitions

  • the present invention relates to an oxyhalide, a preparation method thereof and an all-solid-state lithium battery.
  • All-solid-state lithium batteries have attracted much attention due to their simple structure, high safety, and high energy density. Since all-solid-state lithium batteries use solid electrolytes instead of electrolytes and separators, the batteries are thinner and smaller in size, thereby improving the energy density of the batteries and improving the safety performance of the batteries. Therefore, it is of great significance to develop an all-solid-state lithium battery that can replace traditional lithium-ion batteries.
  • all-solid-state lithium batteries face the following problems: (1) How to meet the transmission problem between the positive and negative electrodes and the electrolyte ions at the electrode level; (2) The positive and negative electrodes cannot maintain very good contact during the cycle like liquids; (3) Lithium metal easily generates lithium dendrites during the charge and discharge process. The existence of these problems leads to poor electrochemical performance of all-solid-state lithium batteries, which is not conducive to their practical application and development.
  • inorganic solid electrolytes offer higher ionic conductivity and stability.
  • inorganic solid electrolyte materials can be categorized as sulfides, oxides, and halides. Sulfide solid electrolytes have high ionic conductivity (> 10 ⁇ 3 S ⁇ cm ⁇ 1 ), but are susceptible to atmospheric moisture, undergoing harmful hydrolysis reactions that significantly reduce ionic conductivity. Furthermore, sulfides suffer from poor oxidative stability, severely limiting their direct use as high-voltage cathode materials.
  • Oxide solid electrolytes offer high air and thermal stability, low manufacturing costs, and ease of large-scale production. However, their mechanical rigidity leads to poor interfacial contact with electrode materials, requiring high-temperature processing or the incorporation of liquid electrolytes for battery assembly. While halide solid electrolytes exhibit high ionic conductivity (> 10 ⁇ 3 S ⁇ cm ⁇ 1 ) at room temperature, they still face challenges with deliquescence and poor stability.
  • Li 4 B 7 O 12 Cl has high ionic conductivity at 300°C.
  • previous reports have shown that a series of byproducts, such as Li 2 B 4 O 7 , are produced during the synthesis of Li 4 B 7 O 12 Cl, which to some extent reduces the conductivity and electrochemical performance of Li 4 B 7 O 12 Cl.
  • the technical problem addressed by the present invention is to overcome the existing technical drawback of difficulty in preparing pure oxyhalides with excellent electrical conductivity and electrochemical properties.
  • the present invention provides an oxyhalide, a preparation method thereof, and an all-solid-state lithium battery.
  • the preparation method of the present invention is simple, has high raw material utilization, and contains no byproducts, making it suitable for industrial production.
  • the prepared oxyhalide exhibits high ionic conductivity and stability, and good interfacial stability with lithium metal.
  • the prepared all-solid-state lithium battery exhibits excellent electrochemical properties.
  • the inventors employed a solid-phase reaction method. During the preparation process, grinding and tableting the raw materials ensures closer contact between the raw materials and reduces side reactions between the raw materials and the reaction tube. Calcination in a vacuum further avoids side reactions. A combination of low-temperature pre-calcination and high-temperature calcination ensures more uniform mixing of the raw materials, more complete reactions, and minimizes the formation of byproducts. Through the synergistic coordination of these technical features, a pure-phase oxyhalide was ultimately produced.
  • the present invention provides a method for preparing an oxyhalide, wherein the chemical formula of the oxyhalide is Li 3 B 7 O 12 ⁇ (LiX)a, X is Cl and/or Br, and 0 ⁇ a ⁇ 1, and the method comprises the following steps:
  • the temperature of the second calcination is 810-860° C., and the time of the second calcination is 12-30 hours;
  • the temperature of the second calcination is 450-800° C. and the time of the second calcination is 12-30 hours.
  • LiX is distributed in the pore structure of the Li 3 B 7 O 12 framework.
  • the lithium halide may be lithium chloride or lithium bromide.
  • the lithium halide is lithium chloride.
  • the lithium halide is lithium bromide.
  • 0 ⁇ a ⁇ 1 or a is 1, such as 0.4, 0.5 or 0.9, more preferably 0.8 ⁇ a ⁇ 0.98.
  • the molar ratio of the lithium chloride, the lithium oxide and the boron oxide may be (0-2):3:7 and does not include 0:3:7, for example, 2:3:7, 1.8:3:7, 1:3:7 or 0.8:3:7, preferably (1.6-1.96):3:7.
  • step (2) when the lithium source is lithium chloride and lithium borate, the boron source is boron oxide and the lithium borate is lithium metaborate, the molar ratio of the lithium chloride, the lithium borate and the boron oxide may be (0-1):3:2 and does not include 0:3:2, for example, 0.4:3:2, 0.5:3:2, 0.9:3:2 or 1:3:2, preferably (0.8-0.98):3:2.
  • the lithium borate may be lithium metaborate (LiBO 2 ), lithium tetraborate (Li 2 B 4 O 7 ) or lithium pentaborate (LiB 5 O 8 ).
  • step (1) and/or step (2) the grinding operation and conditions may be conventional in the art, for example, performed in a mortar.
  • the tableting equipment can be conventional in the art, such as a tablet press.
  • the tableting pressure is preferably 5-15 MPa, such as 10 MPa.
  • the reaction tube is preferably a quartz tube.
  • the vacuum degree of the reaction tube is preferably less than or equal to 10 ⁇ 3 Pa.
  • step (1) and/or step (2) the sealing is generally performed by heating and melting both ends of the reaction tube.
  • the first calcination and the second calcination are generally carried out in a muffle furnace.
  • the rate of increasing the temperature to the temperature of the first calcination may be 30 to 90° C./hour, for example, 60° C./hour.
  • the temperature of the first calcination is preferably 350-450°C, for example 400°C.
  • the first calcination time is preferably 10-15 hours, for example 12 hours.
  • the cooling rate after the first calcination may be 10° C./h to 80° C./h, for example 50° C./h.
  • the rate of increasing the temperature to the temperature of the second calcination may be 30 to 90° C./hour, for example, 60° C./hour.
  • the cooling rate after the second calcination may be 10° C./h to 80° C./h, for example 50° C./h.
  • step (2) when the lithium source is lithium chloride and lithium oxide and the boron source is boron oxide, the temperature of the second calcination is, for example, 830°C, 840°C, 845°C or 850°C, preferably 835-855°C.
  • step (2) when the lithium source is lithium chloride and lithium oxide and the boron source is boron oxide, the time of the second calcination is preferably 15-26 hours, for example 20 hours or 24 hours.
  • step (2) when the lithium source is lithium chloride and lithium borate and the boron source is boron oxide, the temperature of the second calcination is, for example, 500°C, 600°C or 700°C, preferably 480-610°C.
  • step (2) when the lithium source is lithium chloride and lithium borate and the boron source is boron oxide, the time of the second calcination is preferably 15-26 hours, such as 20 hours or 24 hours.
  • the present invention further provides an oxyhalide prepared by the above-mentioned preparation method, wherein the ionic conductivity of the oxyhalide at 25° C. is 0.2-2 mS ⁇ cm ⁇ 1 .
  • the crystal particle size of the oxyhalide is preferably 0.6-5 ⁇ m, more preferably 0.8-1.5 ⁇ m, for example 1 ⁇ m.
  • the ionic conductivity of the oxyhalide at 25° C. is, for example, 0.25 mS ⁇ cm -1 , 0.44 mS ⁇ cm -1 , 0.52 mS ⁇ cm -1 , 0.72 mS ⁇ cm -1 , 0.81 mS ⁇ cm -1 , 0.83 mS ⁇ cm -1 , 0.92 mS ⁇ cm -1 , 1.01 mS ⁇ cm -1 or 1.12 mS ⁇ cm -1 , preferably 0.4-2 mS ⁇ cm -1 .
  • the electronic conductivity of the oxyhalide at 25°C is preferably 1 ⁇ 10-8-1 ⁇ 10-6 S ⁇ cm -1 , such as 3.18 ⁇ 10-7 S ⁇ cm -1 or 6.52 ⁇ 10-7 S ⁇ cm -1 , more preferably 2.5 ⁇ 10-7-5 ⁇ 10-7 S ⁇ cm -1 .
  • the ionic conductivity of the oxyhalide at 30° C. is preferably 0.4-5 mS ⁇ cm ⁇ 1 , for example 1.23 mS ⁇ cm ⁇ 1 .
  • the ionic conductivity of the oxyhalide at 40° C. is preferably 0.6-5 mS ⁇ cm ⁇ 1 , for example 1.17 mS ⁇ cm ⁇ 1 .
  • the ionic conductivity of the oxyhalide at 50° C. is preferably 1-5 mS ⁇ cm ⁇ 1 , for example 2.03 mS ⁇ cm ⁇ 1 .
  • the present invention also provides an all-solid-state lithium battery, which comprises a positive electrode, a solid electrolyte layer, a buffer layer and a negative electrode arranged in sequence;
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer located on the surface of the positive electrode current collector , and the positive electrode active material layer includes LiFePO4 and the oxyhalide as described above; the solid electrolyte layer includes the oxyhalide as described above, and the buffer layer includes Li6PS5Cl ; the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the surface of the negative electrode current collector.
  • the positive electrode current collector may be any material that does not cause chemical changes and has high conductivity.
  • stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel surface-treated with carbon, nickel, titanium, silver, or the like may be used.
  • the thickness of the positive electrode current collector may be conventional in the art, for example, 16 ⁇ m.
  • the mass ratio of the LiFePO 4 to the oxyhalide may be (2-5):1, for example, 3:1.
  • the thickness of the positive electrode active material layer may be 50-500 ⁇ m, for example, 100 ⁇ m.
  • the thickness of the solid electrolyte layer may be 100-1000 ⁇ m, for example, 400 ⁇ m.
  • the thickness of the buffer layer may be 100-1000 ⁇ m, for example, 420 ⁇ m.
  • any material that does not cause chemical changes and Conductive materials for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, aluminum-cadmium alloy, or copper, stainless steel, or aluminum-cadmium alloy surface-treated with carbon, nickel, titanium, or silver can be used.
  • the thickness of the negative electrode current collector may be 4.5-10 ⁇ m, for example, 6 ⁇ m.
  • the negative electrode active material layer includes graphite and/or silicon carbon, such as graphite.
  • the thickness of the negative electrode active material layer may be 50-500 ⁇ m, for example, 100 ⁇ m.
  • the all-solid-state lithium battery further comprises a shell, and the positive electrode, the solid electrolyte layer, the buffer layer and the negative electrode are encapsulated in the shell.
  • the all-solid-state lithium battery refers to a lithium battery that does not contain any liquid.
  • the present invention also provides a method for preparing the all-solid-state lithium battery as described above, which comprises the following steps:
  • the material of the negative electrode active material layer is added to one side of the buffer layer and subjected to a fourth pressing process to obtain the all-solid-state lithium battery.
  • the process further includes: placing the positive electrode current collector on one side of the positive electrode active material layer, placing the negative electrode current collector on one side of the negative electrode active material layer, and performing a fifth pressing process.
  • the first pressing, the second pressing, the third pressing, the fourth pressing and the fifth pressing are generally performed in a solid-state battery mold.
  • the first pressing pressure may be 300-500 MPa, for example 380 MPa.
  • the second pressing pressure may be 200-400 MPa, for example, 250 MPa.
  • the third pressing pressure may be 200-400 MPa, for example, 250 MPa.
  • the fourth pressing pressure may be 200-400 MPa, for example, 250 MPa.
  • the fifth pressing pressure may be 60-180 MPa, for example, 100 MPa.
  • the all-solid-state lithium battery further includes a shell
  • the positive electrode, the solid electrolyte layer, the buffer layer and the negative electrode are encapsulated in the shell.
  • the raw materials and reagents used in the present invention are all commercially available.
  • the reagents and raw materials used in the present invention are commercially available.
  • the method of the present invention has a simple synthesis process, high raw material utilization rate and no by-products, which is conducive to industrial production;
  • the prepared oxyhalides have high ionic conductivity, air stability and thermal stability, and good interfacial stability with lithium metal;
  • the prepared all-solid-state lithium battery has excellent electrochemical properties.
  • FIG1 is a SEM image of the oxyhalide Li 4 B 7 O 12 Cl prepared in Example 1.
  • FIG1 is a SEM image of the oxyhalide Li 4 B 7 O 12 Cl prepared in Example 1.
  • FIG2 is an XRD diagram of the oxyhalides prepared in Examples 1-2 and Comparative Examples 5-7.
  • FIG3 is an XRD pattern of the oxyhalides prepared in Examples 3-5 and Comparative Example 1.
  • the intermediate product was cooled to room temperature at a cooling rate of 50°C/h, and the intermediate product in the quartz tube was taken out, ground and tableted again (the grinding and tableting conditions were the same as in step 1), and then placed in a quartz tube.
  • the quartz tube was evacuated and sealed, and then transferred to a muffle furnace for a second calcination at a heating rate of 60°C/h.
  • the temperature of the second calcination was 845°C, and the time of the second calcination was 22h.
  • the intermediate product was cooled to room temperature at a cooling rate of 50°C/h to obtain a pure phase oxyhalide Li4B7O12Cl .
  • Example 1 Compared with Example 1, except that the temperature of the second calcination in step (2) is adjusted to 830°C, the other operations and conditions are the same as those in Example 1.
  • the intermediate product was cooled to room temperature at a cooling rate of 50°C/h, and the intermediate product in the quartz tube was taken out, ground and tableted again (the grinding and tableting conditions were the same as in step 1), and then placed in a quartz tube.
  • the quartz tube was evacuated and sealed, and then transferred to a muffle furnace for a second calcination at a heating rate of 60°C/h, a second calcination temperature of 500°C, and a second calcination time of 24h. Thereafter, the intermediate product was cooled to room temperature at a cooling rate of 50 °C/h to obtain a pure phase oxyhalide Li4B7O12Cl .
  • Example 3 Compared with Example 3, except that the temperature of the second calcination in step (2) is adjusted to 600°C, the other operations and conditions are the same as those in Example 3.
  • Example 3 Compared with Example 3, except that the temperature of the second calcination in step (2) is adjusted to 700° C., the other operations and conditions are the same as those in Example 3.
  • Example 4 Compared with Example 4, except that the amount of LiCl added in step (1) was adjusted to 0.9 mmol, the other operations and conditions were the same as those in Example 4, and oxyhalide Li 3 B 7 O 12 ⁇ (LiCl) 0.9 was obtained.
  • Example 4 Compared with Example 4, except that LiCl in step (1) is replaced by LiBr, the other operations and conditions are the same as those in Example 4 to obtain oxyhalide Li 4 B 7 O 12 Br.
  • Example 4 Compared with Example 4, except that the amount of LiCl added in step (1) was adjusted to 0.4 mmol, the other operations and conditions were the same as those in Example 4, to obtain oxyhalide Li 3 B 7 O 12 ⁇ (LiCl) 0.4 .
  • Example 4 Compared with Example 4, except that 1mmol LiCl in step (1) was replaced by 0.25mmol LiCl and 0.25mmol LiBr, the other operations and conditions were the same as those in Example 4 to obtain oxyhalide Li 3 B 7 O 12 ⁇ (LiCl) 0.25 (LiBr) 0.25 .
  • LiFePO 4 and the prepared oxyhalide were sand-milled for 20 minutes in a mass ratio of 7.5:2.5 to obtain the material of the positive electrode active material layer;
  • the positive electrode current collector was aluminum foil with a thickness of 16 ⁇ m;
  • the prepared oxyhalide is used as a solid electrolyte material; Li 6 PS 5 Cl is used as a buffer layer material; graphite is used as a negative electrode active material layer material; and the negative electrode current collector is a copper foil with a thickness of 6 ⁇ m.
  • oxyhalide powder was placed in a mold and pressed at a pressure of 380 MPa using a tablet press to obtain a solid electrolyte layer; 42 mg of Li 6 PS 5 Cl was added to one side of the solid electrolyte layer, and a tablet press was used to perform a second pressing at a pressure of 250 MPa to obtain a buffer layer; 10 mg of the material of the positive electrode active material layer was added to the other side of the solid electrolyte layer, and a tablet press was used to perform a third pressing at a pressure of 250 MPa to obtain a positive electrode active material layer; 10 mg of the material of the negative electrode active material layer was added to one side of the buffer layer, and a tablet press was used to perform a fourth pressing at a pressure of 250 MPa to obtain a negative electrode active material layer; finally, a positive electrode current collector was placed on one side of the positive electrode active material layer and a negative electrode current collector was placed on one side of the negative electrode active material layer, and then a tablet press was used to perform
  • the product was cooled to room temperature at a cooling rate of 50°C/h.
  • the intermediate product in the quartz tube was taken out, ground again, and placed in a quartz tube.
  • the quartz tube was evacuated and sealed, and then transferred to a muffle furnace for a second calcination at a heating rate of 60°C/h.
  • the temperature of the second calcination was 845°C and the time of the second calcination was 22h.
  • the product was then cooled to room temperature at a cooling rate of 50°C/h to obtain an oxyhalide with an impurity phase.
  • 2mmol LiCl, 3mmol Li2O and 7mmol B2O3 were weighed according to the stoichiometric ratio, ground conventionally in a mortar, and then pressed into thin slices using a tablet press at a pressure of 10MPa.
  • the slices were placed in a quartz tube, which was evacuated and sealed (vacuum degree ⁇ 10-3 Pa), and then transferred to a muffle furnace for calcination at a heating rate of 60°C/hour, a calcination temperature of 845°C, and a calcination time of 22h.
  • the slices were then cooled to room temperature at a cooling rate of 50°C/h to obtain an oxyhalide with an impurity phase.
  • Example 1 Compared with Example 1, except that the temperature of the first calcination in step (1) was adjusted to 200° C., the other operations and conditions were the same as those in Example 1.
  • Example 1 Compared with Example 1, except that the temperature of the second calcination in step (2) is adjusted to 780°C, the other operations and conditions are the same as those in Example 1.
  • Example 1 Compared with Example 1, except that the temperature of the second calcination in step (2) is adjusted to 870°C, the other operations and conditions are the same as those in Example 1.
  • Example 1 Compared with Example 1, except that the temperature of the second calcination in step (2) is adjusted to 890° C., the other operations and conditions are the same as those in Example 1.
  • Example 3 Compared with Example 3, except that the temperature of the second calcination in step (2) is adjusted to 400° C., the other operations and conditions are the same as those in Example 3.
  • Example 3 Compared with Example 3, except that the temperature of the second calcination in step (2) is adjusted to 900° C., the other operations and conditions are the same as those in Example 3.
  • Figure 1 is a SEM image of the oxyhalide Li 4 B 7 O 12 Cl prepared in Example 1. As can be seen from the figure, the particle size of the crystal particles of Li 4 B 7 O 12 Cl is about 1 micron.
  • Figures 2 and 3 show the XRD patterns of the oxyhalides prepared in the Examples and Comparative Examples, and Table 2 shows the XRD peaks of the samples prepared in the Examples and Comparative Examples.
  • the test results show that no impurities were detected in the oxyhalides prepared in Examples 1-9 , and the XRD patterns showed no significant differences.
  • the oxyhalides prepared in the Comparative Examples showed impurity peaks attributed to Li2B4O7 .
  • the figures also show that the oxyhalides prepared in Examples 1-9 exhibit crystal structures similar to cubic lithium borate (space group F43c), which closely matches PDF#34-0742.
  • the experimental results of the above embodiments and comparative examples show that in the process of preparing oxyhalides, when the calcination environment is not vacuum, or the raw materials are not pressed into tablets, or the first low-temperature calcination is not performed, or the temperature of the first calcination is not within the range of 350-450°C, or the temperature of the second calcination is not within the range of 810-860°C or 450-800°C, the prepared oxyhalides will be impure and contain impure phases.
  • the peak positions listed in Table 2 indicate that the peak intensity of the substance at the corresponding position is higher than 100 particles/second; “/” indicates that the peak intensity of the substance at the corresponding position is lower than 100 particles/second, which means that no peak appears at this position. “Particles/second” represents the number of particles received by the detector per second. The number of ray particles.
  • the oxyhalide Li 4 B 7 O 12 Cl prepared in Example 1 was exposed to air for six months (room temperature) and sintered in air at 300°C in a muffle furnace for 12 hours, and then characterized by XRD.
  • the test results show that all peaks after six months of exposure to air or sintering in air are consistent with those of the initial sample, indicating that Li 4 B 7 O 12 Cl has high air stability and thermal stability.
  • the ion transference number negatively affects the concentration polarization during charge and discharge, thereby increasing the power density of the battery and limiting the movement of anions in the lithium salt.
  • the lithium ion transference number of Li 4 B 7 O 12 Cl was studied by assembling a Li
  • the assembly process of the half-cell is as follows:
  • the lithium metal sheet was rolled into a thin sheet and cut into discs with a 1 mm diameter circular cutter.
  • 40 mg of Li 4 B 7 O 12 Cl powder was placed in a mold and pressed with a tablet press at a pressure of 380 MPa.
  • a pre-cut disc was placed on each side of the Li 4 B 7 O 12 Cl and the tablet was pressed again at a pressure of 100 MPa.
  • the cells were pressed to obtain a Li
  • the Li + transference number (T Li+ ) of the Li 4 B 7 O 12 Cl electrolyte was measured using a Li
  • ⁇ V (0.01 V) is the DC polarization voltage applied to the sample
  • I0 is the initial current
  • Is is the steady-state current
  • the lithium ion transference number of Li 4 B 7 O 12 Cl was calculated to be 0.74.
  • Li symmetric half-cell was subjected to galvanostatic charge-discharge cycling at 50°C and current densities of 0.01 mA ⁇ cm ⁇ 2 and 0.05 mA ⁇ cm ⁇ 2 , respectively, using a multi - channel battery testing system (LAND, CT3002A ) .
  • the symmetric half-cell reached a polarization voltage of 5 V after 40 cycles (80 hours) and 200 cycles (400 hours) at current densities of 0.05 mA ⁇ cm ⁇ 2 and 0.01 mA ⁇ cm ⁇ 2 , respectively.
  • Test results show that the assembled all-solid-state lithium battery achieved an initial discharge capacity of 75 mAh ⁇ g ⁇ 1 and a 100th discharge capacity of 88 mAh ⁇ g ⁇ 1 , respectively.
  • the initial Coulombic efficiency of the ASSLB was 78%.
  • the ASSLB exhibited high cycling stability and reversible capacity. After 180 cycles, the discharge specific capacity reached 83.6 mAh ⁇ g ⁇ 1 and the Coulombic efficiency was 76%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Primary Cells (AREA)

Abstract

本发明提供了一种氧卤化物及其制备方法与全固态锂电池。该制备方法包括：(1)将按化学计量比称取的锂源和硼源的混合物研磨、压片后，置于反应管中，对反应管抽真空、密封后，进行第一次煅烧，第一次煅烧的温度为300-450℃，第一次煅烧的时间为4-20h；(2)第一次煅烧后，冷却至室温，取出反应管内的中间产物，再次进行研磨、压片后，置于反应管中，对反应管抽真空、密封后，进行第二次煅烧，之后冷却至室温。本发明的制备方法简单、原料利用率高且不含有副产物，利于工业化生产；所制备的氧卤化物具有较高的离子电导率和稳定性，与锂金属之间具有较好的界面稳定性；所制备的全固态锂电池具有优异的电化学性能。

Description

一种氧卤化物及其制备方法与全固态锂电池 技术领域
本发明涉及一种氧卤化物及其制备方法与全固态锂电池。
背景技术
全固态锂电池因其结构简单、安全性高、能量密度大而备受关注，全固态锂电池由于使用固态电解质取代了电解液和隔膜，电池更薄且体积更小，从而提升了电池的能量密度，并且电池的安全性能提升。因此，研发一种能够替代传统的锂离子电池的全固态锂电池意义重大。但是全固态锂电池面临以下问题：(1)电极层面上，如何满足正负极与电解质离子的传输问题；(2)循环过程中正负极不能像液体那样保持非常好的接触；(3)金属锂在充放电过程中容易产生锂枝晶，这些问题的存在导致全固态锂电池的电化学性能较差，不利于其实际的应用和发展。
全固态锂电池的核心部分在于作为固态电解质的化合物。目前，有机和无机化合物都已被报道可作为优质电解质，与有机固态电解质相比，无机固态电解质具有更高的离子导电性和稳定性。到目前为止，无机固态电解质材料可分为硫化物、氧化物和卤化物。硫化物固体电解质具有较高离子电导率(>10-3S·cm-1)，但容易受周围大气中水分的影响，发生有害的水解反应，离子电导率严重下降；此外，硫化物氧化稳定性差，严重限制了高压阴极材料的直接利用。氧化物固体电解质具有较高的空气稳定性和热稳定性，制造成本低，易于大规模生产，然而，它们的机械刚性导致与电极材料的界面接触不良，需要高温工艺或流入液态电解质以组装电池。卤化物固态电解质虽然在室温下具有很高的离子电导率(>10-3S·cm-1)，但仍然面临着易潮解和稳定性差的问题。
氧卤化物材料中，由于二价氧离子和卤素离子的结合，既保留了卤素的极性，又保留了氧的强键能，这为未来探索新的电解质材料提供了更多的可 能性。并且根据报道，Li4B7O12Cl在300℃时具有较高的离子电导率。但是，在以往的报道中，在Li4B7O12Cl的合成过程中会产生一系列副产物，例如Li2B4O7，从而在一定程度上降低了Li4B7O12Cl的导电性和电化学性能。
因此，研发一种纯相且导电性和电化学性能优异的氧卤化物材料对于电池领域而言意义非凡。
发明内容
本发明所解决的技术问题在于克服现有技术中存在的难以制备得到纯相以及导电性和电化学性能优异的氧卤化物的缺陷，提供一种氧卤化物及其制备方法与全固态锂电池。本发明的制备方法简单、原料利用率高且不含有副产物，利于工业化生产；所制备的氧卤化物具有较高的离子电导率和稳定性，与锂金属之间具有较好的界面稳定性；所制备的全固态锂电池具有优异的电化学性能。
为了制备得到纯相的氧卤化物，发明人采用了固相反应法进行制备，在制备过程中，通过将原料进行研磨、压片，可以使得各原料之间接触更紧密、减少原料和反应管之间的副反应发生；通过在真空环境中进行煅烧，进一步避免了副反应的发生；通过采用低温预烧和高温煅烧相结合的煅烧方式，使得各原料成分之间混合更均匀、反应更充分，更大程度地避免了副产物的生成。通过各技术特征之间的协同配合，最终制备得到了纯相的氧卤化物。
本发明通过以下技术方案解决上述技术问题：
本发明提供了一种氧卤化物的制备方法，所述氧卤化物的化学式为Li3B7O12·(LiX)a，X为Cl和/或Br，0＜a≤1，其包括以下步骤：
(1)将按化学计量比称取的锂源和硼源的混合物研磨、压片后，置于反应管中，对所述反应管抽真空、密封后，进行第一次煅烧，所述第一次煅烧的温度为300-450℃，所述第一次煅烧的时间为4-20h；
(2)所述第一次煅烧后，冷却至室温，取出所述反应管内的中间产物，再次进行研磨、压片后，置于反应管中，对所述反应管抽真空、密封后，进 行第二次煅烧，之后冷却至室温，得到所述氧卤化物；
当所述锂源为卤化锂和氧化锂并且所述硼源为氧化硼时，所述第二次煅烧的温度为810-860℃，所述第二次煅烧的时间为12-30h；
当所述锂源为卤化锂和硼酸锂并且所述硼源为氧化硼时，所述第二次煅烧的温度为450-800℃，所述第二次煅烧的时间为12-30h。
本发明中，在所述氧卤化物中，LiX分布在Li3B7O12骨架的孔隙结构中。
本发明中，所述卤化锂可为氯化锂或溴化锂。
当所述X为Cl时，所述卤化锂为氯化锂。
当所述X为Br时，所述卤化锂为溴化锂。
本发明中，所述氧卤化物的化学式中，较佳地，0＜a＜1或a为1，例如0.4、0.5或0.9，更佳地0.8＜a＜0.98。
步骤(2)中，当所述锂源为氯化锂和氧化锂并且所述硼源为氧化硼时，所述氯化锂、所述氧化锂和所述氧化硼的摩尔比可为(0-2)：3:7且不包括0:3:7，例如2：3：7、1.8:3:7、1：3：7或0.8：3：7，较佳地为(1.6-1.96):3:7。
步骤(2)中，当所述锂源为氯化锂和硼酸锂、所述硼源为氧化硼且所述硼酸锂为偏硼酸锂时，所述氯化锂、所述硼酸锂和所述氧化硼的摩尔比可为(0-1):3:2且不包括0:3:2，例如0.4：3：2、0.5：3：2、0.9:3:2或1:3:2，较佳地为(0.8-0.98)：3：2。
本发明中，所述硼酸锂可为偏硼酸锂(LiBO2)、四硼酸锂(Li2B4O7)或五硼酸锂(LiB5O8)。
步骤(1)和/或步骤(2)中，所述研磨的操作和条件可为本领域常规，例如在研钵中进行。
步骤(1)和/或步骤(2)中，所述压片的设备可为本领域常规，例如压片机。所述压片的压力较佳地为5-15MPa，例如10MPa。
步骤(1)和/或步骤(2)中，所述反应管较佳地为石英管。
步骤(1)和/或步骤(2)中，所述抽真空后，所述反应管的真空度较佳地小于或等于10-3Pa。
步骤(1)和/或步骤(2)中，一般通过加热熔融所述反应管的两端进行所述密封。
本发明中，所述第一次煅烧和所述第二次煅烧一般在马弗炉内进行。
步骤(1)中，升温至所述第一次煅烧的温度的速率可为30～90℃/小时，例如60℃/小时。
步骤(1)中，所述第一次煅烧的温度较佳地为350-450℃，例如400℃。
步骤(1)中，所述第一次煅烧的时间较佳地为10-15h，例如12h。
步骤(2)中，所述第一次煅烧后的冷却速率可为10℃/h～80℃/h，例如50℃/h。
步骤(2)中，升温至所述第二次煅烧的温度的速率可为30～90℃/小时，例如60℃/小时。
步骤(2)中，所述第二次煅烧后的冷却速率可为10℃/h～80℃/h，例如50℃/h。
步骤(2)中，当所述锂源为氯化锂和氧化锂并且所述硼源为氧化硼时，所述第二次煅烧的温度例如为830℃、840℃、845℃或850℃，较佳地为835-855℃。
步骤(2)中，当所述锂源为氯化锂和氧化锂并且所述硼源为氧化硼时，所述第二次煅烧的时间较佳地为15-26h，例如20h或24h。
步骤(2)中，当所述锂源为氯化锂和硼酸锂并且所述硼源为氧化硼时，所述第二次煅烧的温度例如为500℃、600℃或700℃，较佳地为480-610℃。
步骤(2)中，当所述锂源为氯化锂和硼酸锂并且所述硼源为氧化硼时，所述第二次煅烧的时间较佳地为15-26h，例如20h或24h。
本发明还提供了一种如前所述的制备方法制备的氧卤化物，其中，所述氧卤化物在25℃的离子电导率为0.2-2mS·cm-1。
本发明中，所述氧卤化物的晶体颗粒粒径较佳地为0.6-5μm，更佳地为0.8-1.5μm，例如1μm。
本发明中，所述氧卤化物在25℃的离子电导率例如为0.25mS·cm-1、 0.44mS·cm-1、0.52mS·cm-1、0.72mS·cm-1、0.81mS·cm-1、0.83mS·cm-1、0.92mS·cm-1、1.01mS·cm-1或1.12mS·cm-1，较佳地为0.4-2mS·cm-1。
本发明中，所述氧卤化物在25℃的电子电导率较佳地为1×10-8-1×10-6S·cm-1，例如3.18×10-7S·cm-1或6.52×10-7S·cm-1，更佳地为2.5×10-7-5×10-7S·cm-1。
本发明中，所述氧卤化物在30℃的离子电导率较佳地为0.4-5mS·cm-1，例如1.23mS·cm-1。
本发明中，所述氧卤化物在40℃的离子电导率较佳地为0.6-5mS·cm-1，例如1.17mS·cm-1。
本发明中，所述氧卤化物在50℃的离子电导率较佳地为1-5mS·cm-1，例如2.03mS·cm-1。
本发明还提供了一种全固态锂电池，其包括依次设置的正极、固态电解质层、缓冲层和负极；
其中，所述正极包括正极集流体和位于所述正极集流体的表面的正极活性物质层，所述正极活性物质层包括LiFePO4和如前所述的氧卤化物；所述固态电解质层包括如前所述的氧卤化物，所述缓冲层包括Li6PS5Cl，所述负极包括负极集流体和位于所述负极集流体的表面的负极活性物质层。
本发明中，对于所述正极集流体，可不受限制地使用不引起化学变化且具有高导电性的材料。例如，通常可使用：不锈钢、铝、镍、钛、焙烧碳、或者“用碳、镍、钛、银等表面处理过的铝或不锈钢材料”。
本发明中，所述正极集流体的厚度可为本领域常规，例如16μm。
本发明中，所述正极活性物质层中，所述LiFePO4和所述氧卤化物的质量比可为(2-5)：1，例如3:1。
本发明中，所述正极活性物质层的厚度可为50-500μm，例如100μm。
本发明中，所述固态电解质层的厚度可为100-1000μm，例如400μm。
本发明中，所述缓冲层的厚度可为100-1000μm，例如420μm。
本发明中，对于所述负极集流体，可不受限制地使用不引起化学变化且 具有导电性的材料。例如，可使用：铜、不锈钢、铝、镍、钛、焙烧碳、铝镉合金、或者“用碳、镍、钛或银表面处理过的铜、不锈钢材料或铝镉合金”。
本发明中，所述负极集流体的厚度可为4.5-10μm，例如6μm。
本发明中，所述负极活性物质层包括石墨和/或硅碳，例如石墨。
本发明中，所述负极活性物质层的厚度可为50-500μm，例如100μm。
本发明中，所述全固态锂电池还包括外壳，所述正极、所述固态电解质层、所述缓冲层和所述负极封装在所述外壳中。
本发明中，根据本领域常规，所述全固态锂电池指不含有任何液体的锂电池。
本发明还提供了一种如前所述的全固态锂电池的制备方法，其包括以下步骤：
将所述固态电解质层的材料进行第一压制，得到所述固态电解质层；
将所述缓冲层的材料加入所述固态电解质层的一侧进行第二压制，得到所述缓冲层；
将所述正极活性物质层的材料加入所述固态电解质层的另一侧进行第三压制，得到所述正极活性物质层；
将所述负极活性物质层的材料加入所述缓冲层的一侧进行第四压制，得到所述全固态锂电池。
本发明中，所述第四压制之后，较佳地，还包括：在所述正极活性物质层的一侧放置所述正极集流体、在所述负极活性物质层的一侧放置所述负极集流体以及进行第五压制的过程。
本发明中，所述第一压制、所述第二压制、所述第三压制、所述第四压制和所述第五压制一般在固态电池模具中进行。
本发明中，所述第一压制的压力可为300-500MPa，例如380MPa。
本发明中，所述第二压制的压力可为200-400MPa，例如250MPa。
本发明中，所述第三压制的压力可为200-400MPa，例如250MPa。
本发明中，所述第四压制的压力可为200-400MPa，例如250MPa。
本发明中，所述第五压制的压力可为60-180MPa，例如100MPa。
本发明中，当所述全固态锂电池还包括外壳时，将所述正极、所述固态电解质层、所述缓冲层和所述负极封装在所述外壳中。
本发明所使用原料和试剂均市售可得。
在符合本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：
(1)本发明所述方法合成工艺简单、原料利用率高且不含有副产物，利于工业化生产；
(2)制备的氧卤化物具有较高的离子电导率、空气稳定性和热稳定性，与锂金属之间具有较好的界面稳定性；
(3)所制备的全固态锂电池具有优异的电化学性能。
附图说明
图1为实施例1所制备的氧卤化物Li4B7O12Cl的SEM图。
图2为实施例1-2和对比例5-7所制备的氧卤化物的XRD图。
图3为实施例3-5和对比例1所制备的氧卤化物的XRD图。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
下述实施例和对比例中，所采用的原料的厂家和纯度如下表1所示：
表1
实施例1
(1)按化学计量比称取2mmol LiCl、3mmol Li2O和7mmol B2O3，采用研钵常规研磨后，再采用压片机以10MPa压力压成薄片后，置于石英管中，对石英管抽真空、密封(通过加热熔融石英管的两端进行密封)后(真空度＜10-3Pa)，转移至马弗炉内进行第一次煅烧，升温速率为60℃/小时，第一次煅烧的温度为400℃，第一次煅烧的时间为12h；
(2)第一次煅烧后，冷却至室温，冷却速率为50℃/h，取出石英管内的中间产物，再次进行研磨、压片后(研磨和压片的条件同步骤1)，置于石英管中，对石英管抽真空、密封后，转移至马弗炉内进行第二次煅烧，升温速率为60℃/小时，第二次煅烧的温度为845℃，第二次煅烧的时间为22h，之后冷却至室温，冷却速率为50℃/h，得到纯相氧卤化物Li4B7O12Cl。
实施例2
与实施例1相比，除了将步骤(2)中第二次煅烧的温度调整为830℃之外，其余操作和条件均和实施例1相同。
实施例3
(1)按化学计量比称取1mmol LiCl、3mmol LiBO2和2mmol B2O3，采用研钵常规研磨后，再采用压片机以10MPa压力压成薄片后，置于石英管中，对石英管抽真空、密封(通过加热熔融石英管的两端进行密封)后(真 空度＜10-3Pa)，转移至马弗炉内进行第一次煅烧，升温速率为60℃/小时，第一次煅烧的温度为400℃，第一次煅烧的时间为12h；
(2)第一次煅烧后，冷却至室温，冷却速率为50℃/h，取出石英管内的中间产物，再次进行研磨、压片后(研磨和压片的条件同步骤1)，置于石英管中，对石英管抽真空、密封后，转移至马弗炉内进行第二次煅烧，升温速率为60℃/小时，第二次煅烧的温度为500℃，第二次煅烧的时间为24h，之后冷却至室温，冷却速率为50℃/h，得到纯相氧卤化物Li4B7O12Cl。
实施例4
与实施例3相比，除了将步骤(2)中第二次煅烧的温度调整为600℃之外，其余操作和条件均和实施例3相同。
实施例5
与实施例3相比，除了将步骤(2)中第二次煅烧的温度调整为700℃之外，其余操作和条件均和实施例3相同。
实施例6
与实施例4相比，除了将步骤(1)中LiCl的加入量调整为0.9mmol之外，其余操作和条件均和实施例4相同，得到氧卤化物Li3B7O12·(LiCl)0.9。
实施例7
与实施例4相比，除了将步骤(1)中的LiCl替换为LiBr之外，其余操作和条件均和实施例4相同，得到氧卤化物Li4B7O12Br。
实施例8
与实施例4相比，除了将步骤(1)中LiCl的加入量调整为0.4mmol之外，其余操作和条件均和实施例4相同，得到氧卤化物Li3B7O12·(LiCl)0.4。
实施例9
与实施例4相比，除了将步骤(1)中1mmol LiCl替换为0.25mmol LiCl和0.25mmol LiBr之外，其余操作和条件均和实施例4相同，得到氧卤化物 Li3B7O12·(LiCl)0.25(LiBr)0.25。
实施例10
全固态锂电池的制备
将LiFePO4和制备的氧卤化物按照质量比7.5:2.5的比例用砂磨机砂磨20分钟，得到正极活性物质层的材料；正极集流体为铝箔，厚度为16μm；
将制备的氧卤化物作为固态电解质材料；Li6PS5Cl作为缓冲层材料；石墨作为负极活性物质层的材料；负极集流体为铜箔，厚度为6μm。
首先，将40mg的氧卤化物粉末置于模具中，采用压片机在380MPa的压力下进行第一压制，得到固态电解质层；将42mg的Li6PS5Cl加入固态电解质层的一侧，采用压片机在250MPa的压力下进行第二压制，得到缓冲层；将10mg正极活性物质层的材料加入固态电解质层的另一侧，采用压片机在250MPa的压力下进行第三压制，得到正极活性物质层；将10mg负极活性物质层的材料加入缓冲层的一侧，采用压片机在250MPa的压力下进行第四压制，得到负极活性物质层；最后，在正极活性物质层的一侧放置正极集流体、在负极活性物质层的一侧放置负极集流体，之后采用压片机在100MPa的压力下进行第五压制，制得全固态锂电池；其中，全固态锂电池中，固态电解质层的厚度为400μm，缓冲层的厚度为420μm，正极活性物质层的厚度为100μm，负极活性物质层的厚度为100μm。
对比例1
(1)按化学计量比称取1mmol LiCl、3mmol LiBO2和2mmol B2O3，采用研钵常规研磨后，再采用压片机以10MPa压力压成薄片后，置于石英管中(不进行抽真空与密封的操作)，转移至马弗炉内进行第一次煅烧，升温速率为60℃/小时，第一次煅烧的温度为400℃，第一次煅烧的时间为12h；
(2)第一次煅烧后，冷却至室温，冷却速率为50℃/h，取出石英管内的中间产物，再次进行研磨、压片后(研磨和压片的条件同步骤1)，置于石英管中，转移至马弗炉内进行第二次煅烧，升温速率为60℃/小时，第二次煅烧的温度为500℃，第二次煅烧的时间为24h，之后冷却至室温，冷却速 率为50℃/h，得到有杂相的氧卤化物。
对比例2
(1)按化学计量比称取2mmol LiCl、3mmol Li2O和7mmol B2O3，采用研钵常规研磨后，置于石英管中，对石英管抽真空、密封后(真空度＜10-3Pa)，转移至马弗炉内进行第一次煅烧，升温速率为60℃/小时，第一次煅烧的温度为400℃，第一次煅烧的时间为12h；
(2)第一次煅烧后，冷却至室温，冷却速率为50℃/h，取出石英管内的中间产物，再次进行研磨后，置于石英管中，对石英管抽真空、密封后，转移至马弗炉内进行第二次煅烧，升温速率为60℃/小时，第二次煅烧的温度为845℃，第二次煅烧的时间为22h，之后冷却至室温，冷却速率为50℃/h，得到有杂相的氧卤化物。
对比例3
按化学计量比称取2mmol LiCl、3mmol Li2O和7mmol B2O3，采用研钵常规研磨后，再采用压片机以10MPa压力压成薄片后，置于石英管中，对石英管抽真空、密封后(真空度＜10-3Pa)，转移至马弗炉内进行煅烧，升温速率为60℃/小时，煅烧的温度为845℃，煅烧的时间为22h，之后冷却至室温，冷却速率为50℃/h，得到有杂相的氧卤化物。
对比例4
与实施例1相比，除了将步骤(1)中第一次煅烧的温度调整为200℃之外，其余操作和条件均和实施例1相同。
对比例5
与实施例1相比，除了将步骤(2)中第二次煅烧的温度调整为780℃之外，其余操作和条件均和实施例1相同。
对比例6
与实施例1相比，除了将步骤(2)中第二次煅烧的温度调整为870℃之外，其余操作和条件均和实施例1相同。
对比例7
与实施例1相比，除了将步骤(2)中第二次煅烧的温度调整为890℃之外，其余操作和条件均和实施例1相同。
对比例8
与实施例3相比，除了将步骤(2)中第二次煅烧的温度调整为400℃之外，其余操作和条件均和实施例3相同。
对比例9
与实施例3相比，除了将步骤(2)中第二次煅烧的温度调整为900℃之外，其余操作和条件均和实施例3相同。
效果实施例
(1)结构和形貌分析
图1为实施例1所制备的氧卤化物Li4B7O12Cl的SEM图。从图中可以看出，Li4B7O12Cl的晶体颗粒粒径约为1微米。
(2)XRD表征
图2和图3为实施例和对比例所制备的氧卤化物的XRD图，表2为实施例和对比例所制备样品XRD的出峰情况。根据测试结果可知，实施例1-9所制备的氧卤化物未检测到杂相物质的存在，XRD图谱无明显差别，而对比例所制备的氧卤化物中则存在Li2B4O7的杂质峰。从图中也能看出，实施例1-9所制备的氧卤化物显示出类似于立方络硼酸锂结构(空间群F43c)的晶体结构，这与PDF#34-0742很好地匹配。
通过上述实施例和对比例的实验结果，可知在制备氧卤化物的过程中，当煅烧的环境不是真空、或者不对原料进行压片、或者不进行第一次的低温煅烧、或者第一次煅烧的温度不在350-450℃的范围内、或者第二次煅烧的温度不在810-860℃或450-800℃的范围内时，均会导致所制备的氧卤化物不纯，含有杂相。
表2中所列出的出峰位置表示该物质在对应位置的出峰强度高于100粒子数/秒；“/”代表该物质在对应位置的出峰强度低于100粒子数/秒，即认为该位置处无对应峰出现，其中，“粒子数/秒”代表探测器每秒接受的x 射线粒子数。
表2
(3)离子电导率测试
在室温25℃下，将300mg上述实施例1-9和对比例1-9所制备的氧卤化物粉末先在380Mpa下压制成薄片，然后放入密封的真空石英管中，在600℃下煅烧20h，之后将煅烧后的颗粒转移至模具PEEK套管中，使用电化 学工作站(CHI，650E)进行电化学阻抗测试，外加电压设置为0.05V，频率范围为10-1Hz至106Hz，测试结果见表3。
氧卤化物固态电解质的锂离子电导率计算公式为：离子电导率ρ＝L/RS，L为3mm，S代表半径为5mm的圆的面积，R为阻抗。
表3
实施例1所制备的氧卤化物固态电解质在不同温度下的锂离子电导率见表4。
表4
(4)电子电导率测试
在室温25℃下，将实施例1-2和对比例6-7所制备的氧卤化物固态电解 质粉末置于PEEK套管中，在粉末两端放置两个离子阻断电极，然后施加380Mpa的压力，使用电化学工作站(CHI，650E)进行直流(DC)极化测量，测试在不同极化电压下的电子电导率。电子电导率的计算公式为σe＝LI/SE，σe为电子电导率，L为Li4B7O12Cl电解质的厚度(0.3cm)，S为Li4B7O12Cl电解质的面积(0.785cm2)，E为极化电压(1V)，I为稳态电流。
测试结果见表5。
表5
(5)Li4B7O12Cl的稳定性研究
将实施例1所制备的氧卤化物Li4B7O12Cl分别在空气中暴露六个月(常温)、在马弗炉中于300℃的空气中烧结12小时后，进行XRD表征，根据测试结果可知，暴露在空气中六个月或者在空气中烧结之后，所有峰值都与初始样品的峰值一致，这表明Li4B7O12Cl具有很高的空气稳定性和热稳定性。
(6)Li4B7O12Cl与锂金属之间的界面稳定性研究
采用实施例1制备的氧卤化物Li4B7O12Cl进行研究。
离子迁移数会对充放电过程中的浓度极化产生负面影响，从而提高电池的功率密度并限制锂盐中阴离子的移动。
通过组装Li|Li4B7O12Cl|Li对称半电池，研究了Li4B7O12Cl的锂离子迁移数，半电池的组装过程如下：
将锂金属片擀成薄片，用直径1mm的切圆刀裁成圆片；将40mg的Li4B7O12Cl粉末置于模具中，采用压片机在380MPa的压力下进行压制后，在Li4B7O12Cl的两侧各放置一个事先裁好的圆片，再在100MPa的压力下进 行压制，得到Li|Li4B7O12Cl|Li对称半电池。
使用Li|Li4B7O12Cl|Li电池测量了Li4B7O12Cl电解质的Li+迁移数(TLi+)。恒电位测量在0.05V直流极化电压下进行，以获得初始电流和稳定电流。恒电位测试前的初始电阻(R0)和测量后的电阻(Rs)通过交流阻抗测量获得，频率为10-1Hz至106Hz。电解质的迁移数由下述公式求得：
其中ΔV(0.01V)是施加到样品上的直流极化电压，I0是初始电流，Is是稳定电流。
根据实验结果，计算得出Li4B7O12Cl的锂离子迁移数为0.74。锂离子迁移数越高，相应阴离子的迁移数越低，浓度极化越小，这将阻碍锂枝晶的生长和一些副反应的发生。
为了评估Li4B7O12Cl固体电解质对金属锂的电化学稳定性，使用多通道电池测试系统(LAND，CT3002A)，对组装好的Li|Li4B7O12Cl|Li对称半电池在50℃、0.01mA·cm-2和0.05mA·cm-2的电流密度下分别进行了恒流充放电循环。对称半电池在0.05mA·cm-2和0.01mA·cm-2的电流密度下分别在40个周期(80小时)和200个周期(400小时)后达到5V的极化电压。
(7)全固态锂电池(ASSLB)的电化学性能研究
基于实施例1所制备的Li4B7O12Cl，按照上述方法组装成ASSLB进行研究。电池测试系统(LAND，CT3002A)测试了50℃下LiFePO4@Li4B7O12Cl|Li4B7O12Cl|Li6PS5Cl|石墨ASSLB的恒流充放电特性。
根据测试结果，可知组装的全固态锂电池的初始放电容量和第100次放电容量分别为75mAh·g-1和88mAh·g-1。ASSLB的初始库仑效率为78％。ASSLB具有较高的循环稳定性和可逆容量。经过180次循环后，放电特定容量为83.6mAh·g-1，库仑效率为76％。
虽然以上描述了本发明的具体实施方式，但是本领域的技术人员应当理 解，这仅是举例说明，本发明的保护范围是由所附权利要求书限定的。本领域的技术人员在不背离本发明的原理和实质的前提下，可以对这些实施方式做出多种变更或修改，但这些变更和修改均落入本发明的保护范围。

Claims (10)

  1. 一种氧卤化物的制备方法，其特征在于，所述氧卤化物的化学式为Li3B7O12·(LiX)a，X为Cl和/或Br，0＜a≤1，其包括以下步骤：
    (1)将按化学计量比称取的锂源和硼源的混合物研磨、压片后，置于反应管中，对所述反应管抽真空、密封后，进行第一次煅烧，所述第一次煅烧的温度为300-450℃，所述第一次煅烧的时间为4-20h；
    (2)所述第一次煅烧后，冷却至室温，取出所述反应管内的中间产物，再次进行研磨、压片后，置于反应管中，对所述反应管抽真空、密封后，进行第二次煅烧，之后冷却至室温，得到所述氧卤化物；
    当所述锂源为卤化锂和氧化锂并且所述硼源为氧化硼时，所述第二次煅烧的温度为810-860℃，所述第二次煅烧的时间为12-30h；
    当所述锂源为卤化锂和硼酸锂并且所述硼源为氧化硼时，所述第二次煅烧的温度为450-800℃，所述第二次煅烧的时间为12-30h。
  2. 如权利要求1所述的氧卤化物的制备方法，其特征在于，所述制备方法满足以下条件中的一种或多种：
    (1)步骤(1)和/或步骤(2)中，所述压片的压力为5-15MPa；
    (2)步骤(1)和/或步骤(2)中，所述反应管为石英管；
    (3)步骤(1)和/或步骤(2)中，所述抽真空后，所述反应管的真空度小于或等于10-3Pa；
    (4)所述硼酸锂为偏硼酸锂、四硼酸锂或五硼酸锂；
    (5)所述卤化锂为氯化锂或溴化锂；
    (6)所述氧卤化物的化学式中，0.8＜a＜0.98。
  3. 如权利要求1或2所述的氧卤化物的制备方法，其特征在于，步骤(1)中，所述第一次煅烧的温度为350-450℃；
    和/或，步骤(1)中，所述第一次煅烧的时间为10-15h。
  4. 如权利要求1或2所述的氧卤化物的制备方法，其特征在于，步骤(2)中，当所述锂源为氯化锂和氧化锂并且所述硼源为氧化硼时，所述第二次煅烧的温度为835-855℃；
    和/或，步骤(2)中，当所述锂源为氯化锂和氧化锂并且所述硼源为氧化硼时，所述第二次煅烧的时间为15-26h；
    和/或，步骤(2)中，当所述锂源为氯化锂和氧化锂并且所述硼源为氧化硼时，所述氯化锂、所述氧化锂和所述氧化硼的摩尔比为(1.6-1.96):3:7。
  5. 如权利要求1或2所述的氧卤化物的制备方法，其特征在于，步骤(2)中，当所述锂源为氯化锂和硼酸锂并且所述硼源为氧化硼时，所述第二次煅烧的温度为480-610℃；
    和/或，步骤(2)中，当所述锂源为氯化锂和硼酸锂并且所述硼源为氧化硼时，所述第二次煅烧的时间为15-26h；
    和/或，步骤(2)中，当所述锂源为氯化锂和硼酸锂、所述硼源为氧化硼且所述硼酸锂为偏硼酸锂时，所述氯化锂、所述硼酸锂和所述氧化硼的摩尔比为(0.8-0.98)：3：2。
  6. 一种氧卤化物，其特征在于，其按照权利要求1-5中任一项所述的氧卤化物的制备方法制得，所述氧卤化物在25℃的离子电导率为0.2-2mS·cm-1。
  7. 一种全固态锂电池，其特征在于，其包括依次设置的正极、固态电解质层、缓冲层和负极；
    其中，所述正极包括正极集流体和位于所述正极集流体的表面的正极活性物质层，所述正极活性物质层包括LiFePO4和如权利要求6所述的氧卤化物；所述固态电解质层包括如权利要求6所述的氧卤化物，所述缓冲层包括Li6PS5Cl，所述负极包括负极集流体和位于所述负极集流体的表面的负极活性物质层。
  8. 如权利要求7所述的全固态锂电池，其特征在于，所述全固态锂电池满足以下条件中的一种或多种：
    (1)所述正极活性物质层中，所述LiFePO4和所述氧卤化物的质量比为(2-5)：1；
    (2)所述正极活性物质层的厚度为50-500μm；
    (3)所述固态电解质层的厚度为100-1000μm；
    (4)所述缓冲层的厚度为100-1000μm；
    (5)所述负极活性物质层的厚度为50-500μm。
  9. 一种如权利要求7或8所述的全固态锂电池的制备方法，其特征在于，其包括以下步骤：
    将所述全固态锂电池的固态电解质层的材料进行第一压制，得到所述固态电解质层；
    将所述全固态锂电池的缓冲层的材料加入所述固态电解质层的一侧进行第二压制，得到所述缓冲层；
    将所述全固态锂电池的正极活性物质层的材料加入所述固态电解质层的另一侧进行第三压制，得到所述正极活性物质层；
    将所述全固态锂电池的负极活性物质层的材料加入所述缓冲层的一侧进行第四压制，得到所述全固态锂电池。
  10. 如权利要求9所述的全固态锂电池的制备方法，其特征在于，所述制备方法满足以下条件中的一种或多种：
    (1)所述第四压制之后，还包括：在所述正极活性物质层的一侧放置所述正极集流体、在所述负极活性物质层的一侧放置所述负极集流体以及进行第五压制的过程；
    (2)所述第一压制的压力为300-500MPa；
    (3)所述第二压制的压力为200-400MPa；
    (4)所述第三压制的压力为200-400MPa；
    (5)所述第四压制的压力为200-400MPa；
    (6)所述第五压制的压力为60-180MPa。
PCT/CN2024/104098 2024-04-07 2024-07-05 一种氧卤化物及其制备方法与全固态锂电池 Pending WO2025213595A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020247031874A KR102816302B1 (ko) 2024-04-07 2024-07-05 옥시할라이드 및 이의 제조 방법과 전고체 리튬 배터리

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202410405391.9A CN117985730B (zh) 2024-04-07 2024-04-07 一种氧卤化物及其制备方法与全固态锂电池
CN202410405391.9 2024-04-07

Publications (1)

Publication Number Publication Date
WO2025213595A1 true WO2025213595A1 (zh) 2025-10-16

Family

ID=90890911

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2024/104098 Pending WO2025213595A1 (zh) 2024-04-07 2024-07-05 一种氧卤化物及其制备方法与全固态锂电池

Country Status (2)

Country Link
CN (1) CN117985730B (zh)
WO (1) WO2025213595A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117985730B (zh) * 2024-04-07 2024-05-31 上海交通大学 一种氧卤化物及其制备方法与全固态锂电池
CN119569137A (zh) * 2025-02-07 2025-03-07 江苏正力新能电池技术股份有限公司 正极材料及其制备方法、正极片和电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5332631A (en) * 1990-10-24 1994-07-26 E.I.C. Corp. Solid polymer electrolytes to alleviate voltage delay of lithiium cells
CN112093806A (zh) * 2020-07-30 2020-12-18 浙江工业大学 一种卤化硼酸锂的合成方法
US20210074998A1 (en) * 2017-12-04 2021-03-11 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery, preparing method thereof and rechargeable lithium battery comprising positive electrode including positive active material
CN115207456A (zh) * 2022-07-20 2022-10-18 南京航空航天大学 一种全固态锂电池及其制备方法
CN117985730A (zh) * 2024-04-07 2024-05-07 上海交通大学 一种氧卤化物及其制备方法与全固态锂电池

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108206278A (zh) * 2016-12-20 2018-06-26 宁德时代新能源科技股份有限公司 改性锂离子电池正极材料及其制备方法、锂离子电池
CN112110452B (zh) * 2020-07-30 2022-01-04 浙江工业大学 一种利用气固反应合成卤化硼酸锂的方法
KR102622330B1 (ko) * 2020-08-21 2024-01-09 주식회사 엘지화학 양극 활물질의 제조방법
KR20220070728A (ko) * 2020-11-23 2022-05-31 삼성에스디아이 주식회사 리튬이차전지용 양극활물질, 그 제조방법 및 이를 포함하는 양극을 포함한 리튬이차전지
EP4002510A1 (en) * 2020-11-23 2022-05-25 Samsung SDI Co., Ltd. Positive active material for rechargeable lithium battery, preparing method thereof and rechargeable lithium battery comprising positive electrode including positive active material
KR102907167B1 (ko) * 2022-04-29 2025-12-31 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
CN115852468B (zh) * 2023-03-02 2023-05-23 江门市科恒实业股份有限公司 一种单晶动力型锰酸锂及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5332631A (en) * 1990-10-24 1994-07-26 E.I.C. Corp. Solid polymer electrolytes to alleviate voltage delay of lithiium cells
US20210074998A1 (en) * 2017-12-04 2021-03-11 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery, preparing method thereof and rechargeable lithium battery comprising positive electrode including positive active material
CN112093806A (zh) * 2020-07-30 2020-12-18 浙江工业大学 一种卤化硼酸锂的合成方法
CN115207456A (zh) * 2022-07-20 2022-10-18 南京航空航天大学 一种全固态锂电池及其制备方法
CN117985730A (zh) * 2024-04-07 2024-05-07 上海交通大学 一种氧卤化物及其制备方法与全固态锂电池

Also Published As

Publication number Publication date
CN117985730A (zh) 2024-05-07
CN117985730B (zh) 2024-05-31

Similar Documents

Publication Publication Date Title
CN113097559B (zh) 一种卤化物固态电解质及其制备方法和应用、一种全固态锂离子电池
WO2025213595A1 (zh) 一种氧卤化物及其制备方法与全固态锂电池
CN105140560B (zh) 一种对金属锂稳定的锂离子固体导体及其制备方法以及一种全固态锂二次电池
CN110534802A (zh) 固态电解质及其制备方法和应用
CN118336096A (zh) 一种卤氧化物固态电解质及其制备方法和应用
CN115911530A (zh) 一种锂氮卤化物固态电解质及制备方法与应用
CN111640979B (zh) 一种固态电解质及其制备方法与应用
CN115863559A (zh) 一种高价态金属元素修饰改性的p2型钠离子电池正极材料及制备方法与应用
CN112768756B (zh) 固态电解质材料以及利用该材料制得的复合固态电解质和全固态电池
WO2023130671A1 (zh) 一种复合固态电解质材料及其制备方法和应用
US11063293B2 (en) Increasing ionic conductivity of LiTi2(PS4)3 by Zr doping
CN112259786B (zh) 一种LiBH4-LiI-P2S5三元复合固态电解质及其制备方法
US10807877B2 (en) Increasing ionic conductivity of LiTi2(PS4)3 by Al doping
RU2845045C1 (ru) Оксигалогенид, способ его получения и полностью твердотельная литиевая батарея
KR102816302B1 (ko) 옥시할라이드 및 이의 제조 방법과 전고체 리튬 배터리
CN115051026B (zh) 一种钾离子固体电解质材料及其制备方法与应用
CN114725496B (zh) 固态电解质材料及其制备方法和全固态二次电池
CN111916705B (zh) 一种高性能硅氧化物基复合材料的制备及应用
CN117142855A (zh) 一种Li3N掺杂的石榴石型固态电解质片低温烧结的制备方法
JP2026514198A (ja) オキシハライドおよびその製造方法と全固体リチウム電池
CN113140783A (zh) 一种铷掺杂固态液态混合电解质锂电池结构
CN121536958B (zh) 卤化物固态电解质、其制备方法以及包括卤化物固态电解质的固态电池
CN117594866B (zh) 一种硫氮化物固态电解质及其制备方法和应用
CN119660785B (zh) 一种单斜晶系硫化物电解质及其制备方法和应用
CN115117338B (zh) 一种六方片状钴镍双金属硫化物复合材料及其制备方法、应用

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2024555453

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2024555453

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24934663

Country of ref document: EP

Kind code of ref document: A1