Borate electron compound and preparation method thereof

Abstract

The invention relates to the field of inorganic materials, and discloses a borate electronic compound and a preparation method thereof. The general chemical formula I of the electron compound is [Mb (BO3) n] a + (ae-), in the compound, high-concentration electrons are introduced into a borate compound, all interstitial oxygen ions are replaced by the electrons, the compound can be regarded as the electron compound, [Mb (BO3) n] a + is a cation, and the electrons are anions. The preparation method comprises the following steps: S1, carrying out ball milling on an oxide raw material and a simple substance raw material according to a stoichiometric ratio of an electronic compound; and S2, performing high-temperature roasting in an inert atmosphere to obtain an electron compound of which interstitial oxygen ions are all substituted by electrons. The borate electron compound with all interstitial oxygen ions substituted by electrons is synthesized in one step by combining a mechanochemical method and a high-temperature solid-phase reaction, and the borate electron compound is good in stability and excellent in performance and has important significance on research of basic leading edge and practical application.

Description

Technical Field

[0001] The present invention belongs to the field of inorganic material preparation, and relates to borate electronic compounds and a preparation method thereof. Background Art

[0002] Electronic compounds refer to a class of ionic compound materials with electrons as anions, which have important research value in basic frontiers and practical applications. Currently, both commonly used organic and inorganic electronic compounds have problems of poor chemical and structural stability. Therefore, it is of great significance to develop new electronic compounds with good stability and excellent performance.

[0003] The concept of electronic compounds was first proposed by American scholar J.L. Dye (J.Am.Chem.Soc., 1974, 96, 7203 - 7208. Alkali anions. Preparation and crystal structure of a compound which contains the cryptated sodium cation and the sodium anion), which is composed of alkali metals and organic complexing agents (crown ethers, cryptands, etc.), such as Cs + (18 - crown - 6) 2 e - ,Cs + sandwiched between crown ether and anionic electrons to form a sandwich structure (J.Am.Chem.Soc., 1982, 104, 3781 - 3782. Synthesis of Cesium 18 - Crown - 6: The First Single - Crystal Electride). It should be noted that this type of organic electronic compound can only exist stably at a temperature of about 100K or lower because it reacts easily with water and oxygen in the air.

[0004] In order to explore electronic compounds stable at room temperature and in air, Japanese scholar H. Hosono introduced a high concentration of electrons into the gehlenite 12CaO·7Al 2 O 3 compound, and carried out high - temperature topological reduction of the 12CaO·7Al 2 O 3 single crystal in metal Ca or Ti vapor. All free oxygen ions in the 12CaO·7Al 2 O 3 structure were replaced by electrons (e - ), and the accompanying surface by - products CaO or TiO 2-x needed to be removed by mechanical polishing. Finally, [Ca 24 Al28 O 64 4+ (4e - )Electride (Science, 2003, 301, 626 - 629. High - Density Electron Anions in a Nanoporous Single Crystal: [Ca 24 Al 28 O 64 4+ (4e - ))。The electride [Ca 24 Al 28 O 64 4+ (4e - ) is stable at room temperature and in air and is widely used in fields such as electronic devices, industrial catalysis, and organic synthesis (Chem. Rev., 2021, 121, 3121 - 3185. Advances in Materials and Applications of Inorganic Electrides).

[0005] Subsequently, H. Hosono further introduced electrons into the apatite - type structure Sr 2 La 8 (SiO 4 ) 6 O 2 . Using a quartz tube to vacuum - seal Sr 2 La 8 (SiO 4 ) 6 O 2 and Ti metal, treating at 1200 °C for 24 hours, and then mechanically polishing to remove the surface by - product TiO 2-x , only 10.5% of the channel oxygen ions in the product are replaced by electrons (J. Phys. Chem. Lett. 2015, 6, 4966 - 4971. Electron Confinement in Channel Spaces for One - Dimensional Electride). However, borate electrides have not been reported yet. SUMMARY OF THE INVENTION

[0006] ​​​The present invention provides a borate electron compound and a preparation method thereof. By combining mechanochemistry and high-temperature solid-state reaction, and adjusting the stoichiometric ratio of oxide and elemental raw materials, a borate electron compound in which all interstitial oxygen ions are replaced by electrons is directly synthesized. The specific steps are as follows: The raw materials are ball-milled in an inert atmosphere according to the stoichiometric ratio of the electron compound; the ball-milled powder is subjected to high-temperature calcination treatment in an inert atmosphere, and all interstitial oxygen ions in the product are replaced by electrons.

[0007] The object of the present invention can be achieved by the following solutions:

[0008] In the first aspect, the present invention provides a borate electron compound, and the chemical general formula of the borate electron compound is shown as (I):

[0009] [M b (BO 3 ) n a+ (ae - )(I),

[0010] All interstitial oxygen ions of the borate electron compound are replaced by electrons;

[0011] In formula (I),

[0012] When n is 1, a is 2, M is two elements, and M is X 1 Z 1 , X is one of Mg and Ca, and Z is one of Sc and Y;

[0013] When n is 2, a is 2, M is two elements,

[0014] When M is X 1 Z 2 , X is Ca and Z is Eu;

[0015] When M is X 2 Z 2 , X is one of Na and K, and Z is one of Y, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, and Er;

[0016] When n is 3, a is 2, M is two elements, and M is X 4 Z 1 , X is Ca, and Z is one of Y, La, Pr, Nd, Sm, Gd, Tb, Dy, Er, Tm, and Lu;

[0017] When n is 3, a is 8, M is two elements, and M is X 2 Z 5 , X is Li, and Z is one of Yb and Lu;

[0018] ​When n is 3, a is 10, M is two elements, and M is XZ 6 , X is Li, and Z is one of Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm;

[0019] When n is 8, a is 6, M is two elements, and M is X 3 Z 9 , X is Na, and Z is one of La, Nd, Sm, Eu.

[0020] As an embodiment of the present invention, the electronic compound is selected from one of the following chemical formulas: [MgSc(BO 3 )] 2+ (2e - ), [CaSc(BO 3 )] 2+ (2e - ), [CaY(BO 3 )] 2+ (2e - ), [CaEu 2 (BO 3 ) 2 2+ (2e - ), [Na 2 Y 2 (BO 3 ) 2 2+ (2e - ), [K 2 La 2 (BO 3 ) 2 2+ (2e - ), [K 2 Pr 2 (BO 3 ) 2 2+ (2e - ), [Na 2 Nd 2 (BO 3 ) 2 2+ (2e - ), [K 2 Nd 2 (BO 3 ) 2 2+ (2e - ), [Na 2 Sm 2 (BO 3 ) 2 ​​​​​​​2+ (2e - )、[K 2 Sm 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Eu 2 (BO 3 ) 2 2+ (2e - )、[K 2 Eu 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Gd 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Dy 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Ho 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Er 2 (BO 3 ) 2 2+ (2e - )、[Ca 4 Y(BO 3 ) 3 2+ (2e - )、[Ca 4 La(BO 3 ) 3 2+ (2e - )、[Ca 4 Pr(BO 3 ) 3 2+ (2e - )、[Ca 4 Nd(BO 3 ) 3 2+ (2e - )、[Ca​​​​​​​​​​​4 Sm(BO 3 ) 3 2+ (2e - )、[Ca 4 Gd(BO 3 ) 3 2+ (2e - )、[Ca 4 Tb(BO 3 ) 3 2+ (2e - )、[Ca 4 Dy(BO 3 ) 3 2+ (2e - )、[Ca 4 Er(BO 3 ) 3 2+ (2e - )、[Ca 4 Tm(BO 3 ) 3 2+ (2e - )、[Ca 4 Lu(BO 3 ) 3 2+ (2e - )、[Li 2 Yb 5 (BO 3 ) 3 8+ (8e - )、[Li 2 Lu 5 (BO 3 ) 3 8+ (8e - )、[LiY 6 (BO 3 ) 3 10+ (10e - )、[LiPr 6 (BO 3 ) 3 10+ (10e - )、[LiNd 6 (BO 3 ) 3 10+ (10e - )、[LiSm 6 ​​​​​​​​​​​​(BO 3 ) 3 10+ (10e - )、[LiEu 6 (BO 3 ) 3 10+ (10e - )、[LiGd 6 (BO 3 ) 3 10+ (10e - )、[LiTb 6 (BO 3 ) 3 10+ (10e - )、[LiDy 6 (BO 3 ) 3 10+ (10e - )、[LiHo 6 (BO 3 ) 3 10+ (10e - )、[LiEr 6 (BO 3 ) 3 10+ (10e - )、[LiTm 6 (BO 3 ) 3 10+ (10e - )、[Na 3 La 9 (BO 3 ) 8 6+ (6e - )、[Na 3 Nd 9 (BO 3 ) 8 6+ (6e - )、[Na 3 Sm 9 (BO 3 ) 8 6+ (6e - )、[Na 3 Eu 9 (BO 3 ) 8 6+ (6e - ​​​​​​​​​​​​)。

[0021] As an embodiment of the present invention, the substitution ratio of electrons to oxygen ions is 2:1.

[0022] In a second aspect, the present invention provides a method for preparing the borate electron compound, comprising the following steps:

[0023] S1. Mix the oxide raw material and the elemental raw material according to the stoichiometric ratio of the electron compound, and obtain a precursor after ball milling;

[0024] S2. Calcinate the precursor under an inert atmosphere to obtain the borate electron compound.

[0025] As an embodiment of the present invention, in step S1, the raw materials are the raw materials that have undergone degassing treatment, and the method of degassing treatment includes: heating the raw materials to 800 °C respectively under dynamic vacuum conditions. The degassing treatment can remove the oxygen adsorbed on the surface of the raw materials.

[0026] As an embodiment of the present invention, in step S1, the oxides include B 2 O 3 、Li 2 O, Na 2 O, K 2 O, MgO, CaO, Sc 2 O 3 、Y 2 O 3 、La 2 O 3 、Pr 2 O 3 、Nd 2 O 3 、Sm 2 O 3 、Eu 2 O 3 、Gd 2 O 3 、Tb 2 O 3 、Dy 2 O 3 、Ho 2 O 3 、Er 2 O 3 、Tm 2 O 3 、Yb 2 O 3 、Lu 2 O 3 and at least one of them.

[0027] As an embodiment of the present invention, in step S1, the simple substance includes at least one of B, Li, Na, K, Mg, Ca, Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.

[0028] As an embodiment of the present invention, in step S1, the stoichiometric ratio is:

[0029] When n is 1, a is 2, M is two elements, and M is X 1 Z 1 , and X is one of Mg and Ca, and Z is one of Sc and Y, the stoichiometric ratio is: or or

[0030] When n is 2, a is 2, M is two elements, and M is X 1 Z 2 , and X is Ca and Z is Eu, the stoichiometric ratio is: or or Ca:Eu 2 O 3 :B 2 O 3 = 1:1:1;

[0031] When n is 2, a is 2, M is two elements, and M is X 2 Z 2 , and X is one of Na and K, and Z is one of Y, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, the stoichiometric ratio is: or or X:XO:Z 2 O 3 :B 2 O 3 = 1:1:1:1;

[0032] When n is 3, a is 2, M is two elements, and M is X 4 Z 1 , and X is Ca, and Z is one of Y, La, Pr, Nd, Sm, Gd, Tb, Dy, Er, Tm, Lu, the stoichiometric ratio is: or or

[0033] When n is 3, a is 8, M is two elements, and M is X 2 Z 5 , and X is Li, and Z is one of Yb and Lu, the stoichiometric ratio is: or

[0034] When n is 3 and a is 10, M is two elements, and M is XZ 6 , when X is Li and Z is one of Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, the stoichiometric ratio is:

[0035] When n is 8 and a is 6, M is two elements, and M is X 3 Z 9 , when X is Na and Z is one of La, Nd, Sm, Eu, the stoichiometric ratio is: or

[0036] As an embodiment of the present invention, in step S1, the ball-to-material ratio of the ball milling is 1:1 - 1000:1, the ball milling speed is 50 - 1200 r / min, and the ball milling time is 0.5 - 168 h.

[0037] Further, in step S1, the ball-to-material ratio of the ball milling is 1:1 - 100:1, the ball milling speed is 250 - 500 r / min, and the ball milling time is 0.5 - 8 h.

[0038] In some embodiments, the ball-to-material ratio of the ball milling is 60:1, the ball milling speed is 300 r / min, and the ball milling time is 3 h.

[0039] As an embodiment of the present invention, in step S1, the ball milling is carried out in an inert atmosphere, and the inert atmosphere is argon.

[0040] As an embodiment of the present invention, in step S2, the roasting temperature is 500 - 1500 °C, and the time is 0.5 - 168 h.

[0041] As an embodiment of the present invention, it is characterized in that in step S2, the inert atmosphere includes at least one of vacuum, helium, nitrogen, and argon.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] (1) The present invention combines mechanochemistry and high-temperature solid-state reaction to synthesize a borate electronic compound in which all interstitial oxygen ions are replaced by electrons from raw materials in one step.

[0044] (2) The borate electronic compound prepared by the present invention has good stability (stable in air and water) and excellent performance (all interstitial oxygen is replaced by electrons), which is of great significance for the research of basic frontiers and practical applications. Description of the Drawings

[0045] Other features, objects, and advantages of the present invention will become more apparent from the following detailed description of non - limiting embodiments read in conjunction with the accompanying drawings:

[0046] Figure 1 The borate electronic compound [Ca 4 La(BO 3 ) 3 2+ (2e - ) powder; wherein, the inset is the sample diagram of Example 1;

[0047] Figure 2 The borate electronic compound [Ca 4 La(BO 3 ) 3 2+ (2e - ) powder; electron paramagnetic resonance spectrum diagram;

[0048] Figure 3 The borate electronic compound [Ca 4 La(BO 3 ) 3 2+ (2e - ) powder; thermogravimetric diagram in an oxygen atmosphere. Detailed implementation manners

[0049] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. The following examples are implemented on the premise of the technical solution of the present invention, providing detailed implementation manners and specific operation processes, which will help those skilled in the art to further understand the present invention. It should be noted that the protection scope of the present invention is not limited to the following embodiments. Several adjustments and improvements made under the premise of the concept of the present invention all belong to the protection scope of the present invention.

[0050] In the following examples, the ball - to - material ratio of ball milling is 60:1, and the rotation speed is 300 r / min.

[0051] Example 1

[0052] The raw materials CaO, La 2 O 3 , B 2 O 3 and B powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface - adsorbed oxygen. According to the reaction formula: Mix CaO:La 2 O 3 :B 2 O 3 :B in the ratio of​​​ After being mixed in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0053] Figure 1 This is the X-ray diffraction pattern of the sample. It can be seen from the X-ray diffraction pattern that the obtained black powder is Ca 4 La(BO 3 ) 3 O structure.

[0054] Figure 2 This is the electron paramagnetic resonance spectrum of the sample. The electron paramagnetic resonance spectrum shows a broad signal located at 352 millitesla (g app = 2.073), indicating that electrons are injected into the Ca 4 La(BO 3 ) 3 O lattice.

[0055] Figure 3 This is the thermogravimetric plot of the sample in oxygen. It can be seen from the thermogravimetric plot that the number of included electrons per unit volume in Example 1 is 8.56×10 21 / cm 3 , which means that almost all interstitial oxygen ions are replaced by electrons, that is, the above-mentioned black sample forms an electron compound represented by [Ca 4 La(BO 3 ) 3 2+ (2e - ).

[0056] Comparative Example 1

[0057] The raw materials CaO, La 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: CaO:La 2 O 3 :B 2 O 3 :B were mixed evenly in a stoichiometric ratio. The mixed powder was placed in a tube furnace and held at 1100 °C for 3 hours, 6 hours and 12 hours under argon protection. The main phase of the obtained sample is the raw material phase, and the Ca 4 La(BO 3 ) 3 O phase could not be obtained.

[0058] ​According to the above results, even if the sample is held at 1100 °C for 12 hours, if the raw materials are not ball-milled, it is impossible to form an 4 La(BO 3 ) 3 2+ (2e - ) electron compound.

[0059] Example 2

[0060] The raw materials CaO, La 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing CaO:La 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, it was placed in a ball-milling jar filled with argon and ball-milled for 3 hours. The ball-milled powder was vacuum-sealed in a quartz tube and then held at 1100 °C for 3 hours to obtain a black powder.

[0061] Example 3

[0062] The raw materials CaO, La 2 O 3 , B 2 O 3 and La powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing CaO:La 2 O 3 :La:B 2 O 3 in a stoichiometric ratio, it was placed in a ball-milling jar filled with argon and ball-milled for 3 hours. The ball-milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0063] Example 4

[0064] The raw materials CaO, La 2 O 3 , B 2 O 3 and Ca powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing Ca:CaO:La 2 O 3 :B​2 O 3 After mixing in a stoichiometric ratio of , it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0065] Example 5

[0066] The raw materials CaO, Y 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Y 2 O 3 :B 2 O 3 :B in a stoichiometric ratio of , it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0067] Example 6

[0068] The raw materials CaO, Pr 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Pr 2 O 3 :B 2 O 3 :B in a stoichiometric ratio of , it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0069] Example 7

[0070] The raw materials CaO, Nd 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Nd 2 O 3 :B 2 O 3 :B in a stoichiometric ratio of After being mixed in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0071] Example 8

[0072] The raw materials CaO, Sm 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Sm 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0073] Example 9

[0074] The raw materials CaO, Gd 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Gd 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0075] Example 10

[0076] The raw materials CaO, Tb 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Tb 2 O 3 :B 2 O 3 :B in a After being mixed in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0077] Example 11

[0078] The raw materials CaO, Dy 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Dy 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0079] Example 12

[0080] The raw materials CaO, Er 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Er 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0081] Example 13

[0082] The raw materials CaO, Tm 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Tm 2 O 3 :B 2 O 3 :B in a After being mixed in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0083] Example 14

[0084] The raw materials CaO, Lu 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Lu 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0085] Example 15

[0086] The raw materials MgO, Sc 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing MgO:Sc 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0087] Example 16

[0088] The raw materials CaO, Sc 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Sc 2 O 3 :B 2 O 3 :B in a After being mixed in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0089] Example 17

[0090] The raw materials CaO, Y 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Y 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0091] Example 18

[0092] The raw materials CaO, Eu 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing CaO:Eu 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0093] Example 19

[0094] The raw materials Na 2 O, Y 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing Na 2 O:Y 2 O 3 :B 2 O 3 :B in a After being mixed in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0095] Example 20

[0096] The raw materials K 2 O, La 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: Mix K 2 O:La 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, then place it in a ball milling jar filled with argon and ball mill for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0097] Example 21

[0098] The raw materials K 2 O, Pr 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: Mix K 2 O:Pr 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, then place it in a ball milling jar filled with argon and ball mill for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0099] Example 22

[0100] The raw materials Na 2 O, Nd 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: Mix Na 2 O:Nd 2 O 3 :B2 O 3 :B are mixed in the stoichiometric ratio of and then placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder is placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0101] Example 23

[0102] The raw materials K 2 O, Nd 2 O 3 , B 2 O 3 and B powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: K 2 O:Nd 2 O 3 :B 2 O 3 :B are mixed in the stoichiometric ratio of and then placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder is placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0103] Example 24

[0104] The raw materials Na 2 O, Sm 2 O 3 , B 2 O 3 and B powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: Na 2 O:Sm 2 O 3 :B 2 O 3 :B are mixed in the stoichiometric ratio of and then placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder is placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0105] Example 25

[0106] The raw materials K 2 O, Sm 2 O 3 , B 2 O 3 and B powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: K2 O:Sm 2 O 3 :B 2 O 3 :B in After mixing in the stoichiometric ratio, it is placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder is placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0107] Example 26

[0108] The raw materials Na 2 O, Eu 2 O 3 , B 2 O 3 and B powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: Mix Na 2 O:Eu 2 O 3 :B 2 O 3 :B in the stoichiometric ratio, place it in a ball milling jar filled with argon, and ball mill for 3 hours. The ball milled powder is placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0109] Example 27

[0110] The raw materials K 2 O, Eu 2 O 3 , B 2 O 3 and B powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: Mix K 2 O:Eu 2 O 3 :B 2 O 3 :B in the stoichiometric ratio, place it in a ball milling jar filled with argon, and ball mill for 3 hours. The ball milled powder is placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0111] Example 28

[0112] The raw materials Na 2 O, Gd 2 O 3 , B 2 O 3Powders of Na and B were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the adsorbed oxygen on the surface. According to the reaction formula: Na 2 O:Gd 2 O 3 :B 2 O 3 :B were mixed in a stoichiometric ratio and then placed in a ball-milling jar filled with argon gas, and ball-milled for 3 hours. The ball-milled powder was placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0113] Example 29

[0114] The raw materials of Na 2 O, Dy 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the adsorbed oxygen on the surface. According to the reaction formula: Na 2 O:Dy 2 O 3 :B 2 O 3 :B were mixed in a stoichiometric ratio and then placed in a ball-milling jar filled with argon gas, and ball-milled for 3 hours. The ball-milled powder was placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0115] Example 30

[0116] The raw materials of Na 2 O, Ho 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the adsorbed oxygen on the surface. According to the reaction formula: Na 2 O:Ho 2 O 3 :B 2 O 3 :B were mixed in a stoichiometric ratio and then placed in a ball-milling jar filled with argon gas, and ball-milled for 3 hours. The ball-milled powder was placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0117] Example 31

[0118] The raw materials of Na 2 O, Er 2 O3 and B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: Na 2 O:Er 2 O 3 :B 2 O 3 :B were mixed in a stoichiometric ratio of , placed in a ball milling jar filled with argon, and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0119] Example 32

[0120] The raw materials Li 2 O, Yb 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: Li 2 O:Yb 2 O 3 :B 2 O 3 :B were mixed in a stoichiometric ratio of , placed in a ball milling jar filled with argon, and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0121] Example 33

[0122] The raw materials Li 2 O, Lu 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: Li 2 O:Lu 2 O 3 :B 2 O 3 :B were mixed in a stoichiometric ratio of , placed in a ball milling jar filled with argon, and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0123] Example 34

[0124] The raw materials Li 2 O, Y 2 O 3 , B 2 O 3 and Y powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: Li 2 O:Y 2 O 3 :Y:B 2 O 3 are mixed in the chemical stoichiometric ratio of , placed in a ball milling jar filled with argon, and ball milled for 3 hours. The ball milled powder is placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0125] Example 35

[0126] The raw materials Li 2 O, Pr 2 O 3 , B 2 O 3 and Pr powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: Li 2 O:Pr 2 O 3 :Pr:B 2 O 3 are mixed in the chemical stoichiometric ratio of , placed in a ball milling jar filled with argon, and ball milled for 3 hours. The ball milled powder is placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0127] Example 36

[0128] The raw materials Li 2 O, Nd 2 O 3 , B 2 O 3 and Nd powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: Li 2 O:Nd 2 O 3 :Nd:B 2 O 3 are mixed in the chemical stoichiometric ratio of After mixing in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0129] Example 37

[0130] The raw materials Li 2 O, Sm 2 O 3 , B 2 O 3 and Sm powder were separately heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: Mix Li 2 O:Sm 2 O 3 :Sm:B 2 O 3 in a stoichiometric ratio, then placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0131] Example 38

[0132] The raw materials Li 2 O, Eu 2 O 3 , B 2 O 3 and Eu powder were separately heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: Mix Li 2 O:Eu 2 O 3 :Eu:B 2 O 3 in a stoichiometric ratio, then placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0133] Example 39

[0134] The raw materials Li 2 O, Gd 2 O 3 , B 2 O 3 and Gd powder were separately heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: Mix Li2 O:Gd 2 O 3 :Gd:B 2 O 3 After mixing in the stoichiometric ratio of , it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0135] Example 40

[0136] The raw materials Li 2 O, Tb 2 O 3 , B 2 O 3 and Tb powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: Mix Li 2 O:Tb 2 O 3 :Tb:B 2 O 3 in the stoichiometric ratio of , place it in a ball milling jar filled with argon, and ball mill for 3 hours. The ball milled powder is placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0137] Example 41

[0138] The raw materials Li 2 O, Dy 2 O 3 , B 2 O 3 and Dy powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: [LiDy 6 (BO 3 ) 3 10+ (10e - ), mix Li 2 O:Tb 2 O 3 :Tb:B 2 O 3 in the stoichiometric ratio of , place it in a ball milling jar filled with argon, and ball mill for 3 hours. The ball milled powder is placed in a tube furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0139] Example 42

[0140] ​The raw materials Li 2 O, Ho 2 O 3 , B 2 O 3 and Ho powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing Li 2 O:Ho 2 O 3 :Ho:B 2 O 3 in a stoichiometric ratio of , it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0141] Example 43

[0142] The raw materials Li 2 O, Er 2 O 3 , B 2 O 3 and Er powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing Li 2 O:Er 2 O 3 :Er:B 2 O 3 in a stoichiometric ratio of , it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0143] Example 44

[0144] The raw materials Li 2 O, Tm 2 O 3 , B 2 O 3 and Tm powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove the surface adsorbed oxygen. According to the reaction formula: After mixing Li 2 O:Tm 2 O 3 :Tm:B 2 O 3 in a stoichiometric ratio of After being mixed in a stoichiometric ratio, it was placed in a ball milling jar filled with argon and ball milled for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0145] Example 45

[0146] The raw materials Na 2 O, La 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing Na 2 O:La 2 O 3 :B 2 O 3 :B in a stoichiometric ratio and placing it in a ball milling jar filled with argon, ball milling for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0147] Example 46

[0148] The raw materials Na 2 O, Nd 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing Na 2 O:Nd 2 O 3 :B 2 O 3 :B in a stoichiometric ratio and placing it in a ball milling jar filled with argon, ball milling for 3 hours. The ball milled powder was placed in a tube furnace and held at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0149] Example 47

[0150] The raw materials Na 2 O, Sm 2 O 3 , B 2 O 3 and B powder were respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: After mixing Na 2O:Sm 2 O 3 :B 2 O 3 :B in After mixing in a stoichiometric ratio and placing in a ball milling jar filled with argon, ball milling is carried out for 3 hours. The ball milled powder is placed in a tubular furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0151] Example 48

[0152] The raw materials Na 2 O, Eu 2 O 3 , B 2 O 3 and B powder are respectively heated to 800 °C under dynamic vacuum conditions for degassing treatment to remove surface adsorbed oxygen. According to the reaction formula: Mix Na 2 O:Eu 2 O 3 :B 2 O 3 :B in a stoichiometric ratio, place in a ball milling jar filled with argon, ball mill for 3 hours. The ball milled powder is placed in a tubular furnace and kept at 1100 °C for 3 hours under argon protection to obtain a black powder.

[0153] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A borate electronic compound, characterized in that, the chemical general formula of the borate electronic compound is shown as (I): [M b (BO 3 ) n a+ (ae - )(I),​ all interstitial oxygen ions of the borate electronic compound are replaced by electrons; In formula (I), When n is 1, a is 2, M is two elements, and M is X 1 Z 1 , X is one of Mg and Ca, and Z is one of Sc and Y; when n is 2, a is 2, and M is two elements, M is X 1 Z 2 When M is X, X is Ca and Z is Eu; M is X 2 Z 2 When M is X, X is one of Na and K, and Z is one of Y, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, and Er; When n is 3, a is 2, M is two elements, and M is X 4 Z 1 , X is Ca, and Z is one of Y, La, Pr, Nd, Sm, Gd, Tb, Dy, Er, Tm, Lu; When n is 3, a is 8, M is two elements, and M is X 2 Z 5 , X is Li, and Z is one of Yb and Lu; When n is 3, a is 10, M is two elements, and M is XZ 6 , X is Li, and Z is one of Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm; When n is 8, a is 6, M is two elements, M is X 3 Z 9 , X is Na, and Z is one of La, Nd, Sm, and Eu.

2. The electronic compound according to claim 1, characterized in that, The electronic compound is selected from one of the following chemical formulas: [MgSc(BO 3 )] 2+ (2e - )、[CaSc(BO 3 )] 2+ (2e - )、[CaY(BO 3 )] 2+ (2e - )、[CaEu 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Y 2 (BO 3 ) 2 2+ (2e - )、[K 2 La 2 (BO 3 ) 2 2+ (2e - )、[K 2 Pr 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Nd 2 (BO 3 ) 2 2+ (2e - )、[K 2 Nd 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Sm 2 (BO 3 ) 2 2+ (2e - )、[K 2 Sm 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Eu 2 (BO 3 ) 2 2+ (2e - )、[K​​​​​​​​​ 2 Eu 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Gd 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Dy 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Ho 2 (BO 3 ) 2 2+ (2e - )、[Na 2 Er 2 (BO 3 ) 2 2+ (2e - )、[Ca 4 Y(BO 3 ) 3 2+ (2e - )、[Ca 4 La(BO 3 ) 3 2+ (2e - )、[Ca 4 Pr(BO 3 ) 3 2+ (2e - )、[Ca 4 Nd(BO 3 ) 3 2+ (2e - )、[Ca 4 Sm(BO 3 ) 3 2+ (2e - )、[Ca 4 Gd(BO 3 ) 3 2+ (2e - )、[Ca 4 Tb(BO 3 ) 3 2+ ​​​​​​​​​​​​(2e - )、[Ca 4 Dy(BO 3 ) 3 2+ (2e - )、[Ca 4 Er(BO 3 ) 3 2+ (2e - )、[Ca 4 Tm(BO 3 ) 3 2+ (2e - )、[Ca 4 Lu(BO 3 ) 3 2+ (2e - )、[Li 2 Yb 5 (BO 3 ) 3 8+ (8e - )、[Li 2 Lu 5 (BO 3 ) 3 8+ (8e - )、[LiY 6 (BO 3 ) 3 10+ (10e - )、[LiPr 6 (BO 3 ) 3 10+ (10e - )、[LiNd 6 (BO 3 ) 3 10+ (10e - )、[LiSm 6 (BO 3 ) 3 10+ (10e - )、[LiEu 6 (BO 3 ) 3 10+ (10e - )、[LiGd 6 (BO 3 ) 3 10+ (10e​​​​​​​​​​​​ - )、[LiTb 6 (BO 3 ) 3 10+ (10e - )、[LiDy 6 (BO 3 ) 3 10+ (10e - )、[LiHo 6 (BO 3 ) 3 10+ (10e - )、[LiEr 6 (BO 3 ) 3 10+ (10e - )、[LiTm 6 (BO 3 ) 3 10+ (10e - )、[Na 3 La 9 (BO 3 ) 8 6+ (6e - )、[Na 3 Nd 9 (BO 3 ) 8 6+ (6e - )、[Na 3 Sm 9 (BO 3 ) 8 6+ (6e - )、[Na 3 Eu 9 (BO 3 ) 8 6+ (6e - )。​​​​​​​​​ 3. The electronic compound according to claim 1, characterized in that, the substitution ratio of electrons to oxygen ions is 2:

1.

4. A preparation method of a borate electronic compound according to any one of claims 1-3, characterized in that, it includes the following steps: S1. Mix the oxide raw material and the elemental raw material according to the stoichiometric ratio of the electronic compound, and obtain a precursor after ball milling; S2. Calcinate the precursor under an inert atmosphere to obtain the borate electronic compound.

5. The preparation method according to claim 4, characterized in that, In step S1, the oxide includes B 2 O 3 、Li 2 O、Na 2 O、K 2 O、MgO、CaO、Sc 2 O 3 、Y 2 O 3 、La 2 O 3 、Pr 2 O 3 、Nd 2 O 3 、Sm 2 O 3 、Eu 2 O 3 、Gd 2 O 3 、Tb 2 O 3 、Dy 2 O 3 、Ho 2 O 3 、Er 2 O 3 、Tm 2 O 3 、Yb 2 O 3 、Lu 2 O 3 and at least one of them.

6. The preparation method according to claim 4, characterized in that, in step S1, the element includes at least one of B, Li, Na, K, Mg, Ca, Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.

7. The preparation method according to claim 4, characterized in that, in step S1, the stoichiometric ratio is: n is 1, a is 2, M is two elements, and M is X 1 Z 1 When X is one of Mg and Ca, and Z is one of Sc and Y, the stoichiometric ratio is: or or n is 2, a is 2, M is two elements, M is X 1 Z 2 When X is Ca and Z is Eu, the stoichiometric ratio is: or or Ca:Eu 2 O 3 :B 2 O 3 = 1:1:1; n is 2, a is 2, M is two elements, M is X 2 Z 2 , when X is one of Na and K, and Z is one of Y, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, and Er, the stoichiometric ratio is: or or X:XO:Z 2 O 3 :B 2 O 3 = 1:1:1:1; n is 3, a is 2, M is two elements, and M is X 4 Z 1 , when X is Ca and Z is one of Y, La, Pr, Nd, Sm, Gd, Tb, Dy, Er, Tm, Lu, the stoichiometric ratio is: or or n is 3, a is 8, M is two elements, and M is X 2 Z 5 , when X is Li and Z is one of Yb and Lu, the stoichiometric ratio is: or When n is 3 and a is 10, M is two elements, and M is XZ 6 , when X is Li and Z is one of Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, the stoichiometric ratio is: When n is 8, a is 6, M is two elements, M is X 3 Z 9 , when X is Na and Z is one of La, Nd, Sm, Eu, the stoichiometric ratio is: or 8. The preparation method according to claim 4, characterized in that, in step S1, the ball-to-material ratio of the ball milling is 1:1-1000:1, the ball milling rotation speed is 50-1200 r / min, and the ball milling time is 0.5-168 h.

9. The preparation method according to claim 4, characterized in that, in step S2, the calcination temperature is 500-1500 °C, and the time is 0.5-168 h.

10. The preparation method according to claim 4, characterized in that, in step S2, the inert atmosphere includes at least one of vacuum, helium, nitrogen, and argon.

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