CN113526474B - Lithium nitride particles, and method and apparatus for producing same - Google Patents
Lithium nitride particles, and method and apparatus for producing same Download PDFInfo
- Publication number
- CN113526474B CN113526474B CN202011616707.7A CN202011616707A CN113526474B CN 113526474 B CN113526474 B CN 113526474B CN 202011616707 A CN202011616707 A CN 202011616707A CN 113526474 B CN113526474 B CN 113526474B
- Authority
- CN
- China
- Prior art keywords
- lithium
- nitride particles
- lithium nitride
- nitrogen
- vacuum
- 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.)
- Active
Links
- 239000002245 particle Substances 0.000 title claims abstract description 138
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims description 37
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 140
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 132
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 48
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 17
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 15
- 238000009396 hybridization Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 230000009467 reduction Effects 0.000 claims description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000004484 Briquette Substances 0.000 claims description 14
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 239000011863 silicon-based powder Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 4
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 4
- 239000005997 Calcium carbide Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910001120 nichrome Inorganic materials 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 41
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 16
- 239000000292 calcium oxide Substances 0.000 description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 7
- 229910001947 lithium oxide Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- GRQJZSJOACLQOV-UHFFFAOYSA-N [Li].[N] Chemical compound [Li].[N] GRQJZSJOACLQOV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 102100034013 Gamma-glutamyl phosphate reductase Human genes 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- -1 nitrogen anions Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 1
- 101001133924 Homo sapiens Gamma-glutamyl phosphate reductase Proteins 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910006389 Li—N Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0607—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with alkali metals
- C01B21/061—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with alkali metals with lithium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/04—Crucible or pot furnaces adapted for treating the charge in vacuum or special atmosphere
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details peculiar to crucible or pot furnaces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details peculiar to crucible or pot furnaces
- F27B14/14—Arrangements of heating devices
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/04—Crucible or pot furnaces adapted for treating the charge in vacuum or special atmosphere
- F27B2014/045—Vacuum
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
Abstract
The invention relates to lithium nitride particles, a preparation method and preparation equipment thereof. Aiming at the problems of high preparation cost, low production efficiency and large particle size of lithium nitride in the prior art, the invention provides a preparation method of lithium nitride particles, wherein a hybrid auxiliary agent is prepared firstly, then a lithium source and the hybrid auxiliary agent are uniformly mixed and subjected to thermal decomposition to generate clinker, the clinker is subjected to vacuum thermal reduction reaction with a reducing agent to generate metal lithium vapor, and finally high-purity nitrogen is introduced to react with the metal lithium vapor to prepare the lithium nitride particles. According to the invention, the vacuum thermal reduction reaction and the synthesis of lithium nitride particles are continuously carried out by precisely regulating and controlling the conditions of the hybridization auxiliary agent ratio, the thermal reduction reaction temperature, the vacuum degree, the clinker amount, the reducing agent, the nitrogen flow and the like, so that the lithium nitride particles with smaller particle size are prepared by utilizing the gas phase reaction of lithium vapor and nitrogen.
Description
Technical Field
The invention relates to lithium nitride particles, a preparation method and preparation equipment thereof, in particular to nanoscale lithium nitride particles, and a preparation method and preparation equipment for synthesizing the lithium nitride particles by using a gas phase reaction method.
Background
Lithium nitride (Li) 3 N) is a metal nitride, and is also the only stable binary compound formed by alkali metal and nitrogen, which belongs to the hexagonal system, lithium-nitrogen layers composed of lithium and nitrogen atoms exist in the lattice structure, and one lithium layer exists between every two lithium-nitrogen layers. In the lithium nitride cell, the distance between Li-N was 213pm, close to the sum of the ionic radii of lithium ions and nitrogen anions, and each lithium-nitrogen layer was spaced 194pm from the adjacent lithium layer, indicating that lithium nitride is an ionic compound. Li 3 N has the special physical characteristics, so that the N has excellent performance and can be widely applied to the fields of energy storage, catalysis and hydrogen storage. Li 3 N is used as a fast ion conductor with excellent conductivity and can be used as a solid electrolyte and a positive electrode lithium supplement additive. In addition, lithium nitride can be used as a catalyst to efficiently convert hexagonal boron nitride to cubic boron nitride. In recent years, it has become possible to provide,researchers have found that lithium nitride has certain advantages for use as a hydrogen storage material, compared to conventional hydrogen storage materials, li 3 The hydrogen storage mass fraction of N can reach 10.4%, and the hydrogen storage performance is greatly improved.
At normal temperature, lithium metal can slowly generate lithium nitride when exposed to air, but the generation rate of the lithium nitride in a space filled with nitrogen is 10-15 times faster than that in the air. Therefore, whether lithium nitride is produced industrially or in a laboratory, lithium metal is generally passed through a nitrogen gas stream in a molten state so that the lithium metal reacts with the nitrogen gas to produce lithium nitride. However, the process for industrially preparing lithium nitride causes low utilization rate of metal lithium and poor production efficiency; and the lithium nitride prepared by the process is massive solid or particles with millimeter-sized dimensions, and the service performance is seriously influenced. At present, the particle size of lithium nitride particles sold in the market is too large, such as 150-mesh lithium nitride particles with the particle size of 83.4 μm sold by Merlne Biotechnology Limited; for example, lithium nitride with a particle size of 208.4 μm and a particle size of 60 meshes is sold by Bailingwei technologies, inc. of Beijing, it can be seen that the mass production of lithium nitride with a particle size of nano-scale to several micrometers is still in the blank area of the market.
Journal of university of Physician university of Lanzhou entitled "Li 3 Study on the Synthesis and Hydrogen absorption and desorption Properties of N, wherein Li 3 The preparation steps of N are as follows: placing the lithium metal with the purity of more than 99.99 percent in a closed container with air isolation and controllable temperature, heating a resistance wire to 200 ℃ to ensure that the lithium metal becomes molten state, introducing high-purity nitrogen with the pressure of 0.1MPa, and preserving heat for 12 hours to obtain the lithium nitride simple substance. The process has the following defects: firstly, the lithium source is derived from metal lithium, and the production cost is greatly increased for industrial production; secondly, high-purity nitrogen is introduced into the metal lithium in a molten state to prepare the lithium nitride, so that the problem of limited chemical reaction area in a gas-liquid phase state exists, the reaction of the nitrogen and the metal lithium liquid is insufficient, and the utilization rate of lithium metal is low; finally, the lithium nitride particles produced by the process have large particle size, and the service performance is influenced.
Chinese patent publication No. CN1258239C discloses a preparation method of a novel lithium ion battery cathode material, which comprises a preparation method of pure-phase lithium nitride, wherein metal lithium is put in nitrogen flow which is subjected to purification treatment of dehydration, deoxidation and decarbonation, the temperature is raised to 200-700 ℃, the metal lithium is melted to form metal lithium liquid, and the pure-phase lithium nitride with the particle size of 300 meshes and the particle size of 41.7 mu m is synthesized through gas-liquid phase chemical reaction. The process has the following defects: high-purity metal lithium is used as a lithium source, so that the cost is high; the gas-liquid phase reaction is carried out on the high-purity nitrogen and the molten metal lithium liquid, so that the production efficiency is greatly reduced, and the lithium source cannot be fully utilized.
Chinese patent publication No. CN1300871C discloses a reversible lithium-deintercalating material for a lithium ion battery cathode and a preparation method thereof, the process comprises a preparation method of lithium nitride, wherein a metallic lithium piece is promoted to react with metallic lithium by raising the temperature under a high-purity nitrogen atmosphere, a silver white lithium piece is gradually turned into dark red, and then a product after the reaction is crushed to obtain lithium nitride particles. The lithium nitride prepared by the process has the problems of insufficient reaction of metal lithium and low purity of the obtained lithium nitride particles.
Disclosure of Invention
Aiming at the problems of high preparation cost, low production efficiency and large particle size of lithium nitride in the prior art, the invention provides a preparation method and preparation equipment of lithium nitride particles.
The technical scheme adopted by the invention is as follows:
[1] a preparation method of lithium nitride particles is characterized by comprising the following steps:
(1) A step of preparing hybrid auxiliary agent, wherein calcium hydroxide and aluminum hydroxide are heated and then cooled, and ball milling is carried out to obtain the hybrid auxiliary agent with a chemical formula of xCaO-yAl 2 O 3 The hybrid additive of (1), wherein x and y are mass fractions, x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y =1;
(2) A step of thermal decomposition of a lithium raw material, wherein the hybrid additive and the lithium raw material are uniformly mixed and pressed, and then are subjected to thermal decomposition to obtain clinker;
(3) A vacuum thermal reduction step, wherein the clinker is uniformly mixed with a reducing agent and pressed into a briquette, and the briquette is subjected to vacuum thermal reduction in a vacuum reduction furnace to generate metal lithium vapor;
(4) And synthesizing lithium nitride particles, wherein the metal lithium vapor is introduced into a reaction bin, and nitrogen and the metal lithium vapor are in contact reaction to generate the lithium nitride particles.
[2]According to [1]The preparation method of the lithium nitride particles is characterized in that in the step (1), calcium hydroxide and aluminum hydroxide are uniformly mixed, the mixture is heated to 500-700 ℃ at the heating rate of 1-10 ℃/min under the vacuum degree of 1-20Pa, the temperature is kept for 2-4h, and after cooling, ball milling is carried out to obtain the hybrid auxiliary agent xCaO-yAl 2 O 3 Wherein x and y are preferably 0.1-0.9, and x + y =1;
wherein the hybrid additive xCaO yAl 2 O 3 The particle diameter D50 of the particles is 10.0 μm or less, D50 or less 80.0 μm, preferably 10.0 μm or less, D50 or less 30.0 μm, more preferably 10.3 μm or less, D50 or less 29.5 μm.
[3] The preparation method of the lithium nitride particles according to the item [1], which is characterized in that in the step (2), the hybrid auxiliary agent and a lithium raw material are uniformly mixed, pressed into a cluster under the pressure of 30-100MPa, heated to 500-900 ℃ at the heating rate of 1-10 ℃/min under the vacuum degree of 0.1-10Pa for thermal decomposition, the heat preservation time is 4-10h, and after the reaction is finished, ball milling is carried out to obtain clinker;
the lithium raw material is one or more than two of lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium peroxide and lithium nitrate, and preferably lithium carbonate and lithium hydroxide;
wherein, the grain diameter D50 of the ball-milled clinker is not less than 10.0 μm and not more than 45.0 μm, preferably not less than 10.0 μm and not more than 20.0 μm, more preferably not less than 10.2 μm and not more than 19.8 μm; the mass ratio of the hybridization auxiliary agent to the lithium raw material is (0.5-1.0): 1, preferably (0.75-0.95): 1.
[4] the method for preparing lithium nitride particles according to [1], characterized in that in step (3), the clinker is uniformly mixed with a reducing agent, the mixture is made into an agglomerate under the pressure of 30-100MPa, the agglomerate is heated to 700-1000 ℃ at the heating rate of 1-10 ℃/min under the vacuum degree of 0.1-10Pa, the temperature is kept for 4-8h, and vacuum thermal reduction is carried out in a vacuum reduction furnace to generate metal lithium vapor;
wherein the diameter of the block mass is 20mm-30mm, and the mass is 40-80 g/block.
[5] The method for preparing lithium nitride particles according to [1], wherein in the step (3), the reducing agent is one or more of aluminum powder, silicon powder, iron powder, ferrosilicon, carbon powder, silicoaluminums powder, calcium carbide, ferrosilicon and magnesium powder, preferably aluminum powder, silicon powder and silicoaluminums powder; wherein the mass ratio of the clinker to the reducing agent is 1: (0.1-0.5), preferably 1: (0.2-0.3).
[6] The method for preparing lithium nitride particles according to [1], wherein in the step (4), the metallic lithium vapor enters a reaction bin, the nitrogen flow is adjusted, the nitrogen fully contacts with the metallic lithium vapor to carry out gas phase reaction, lithium nitride particles are generated, and the lithium nitride particles are packaged and sealed in a bag under inert gas;
wherein the nitrogen flow rate is 0.10-0.60L/min, preferably 0.18-0.58L/min; the temperature in the reaction bin is 300-500 ℃, and the purity of the nitrogen is 99.0% -99.99%; the inert gas is nitrogen or argon.
[7] The method for producing lithium nitride particles according to item [1], wherein the lithium nitride particles have a particle diameter of 0.05 to 0.50 μm, preferably 0.10 to 0.30 μm, a purity of 99.0 to 99.4%, and a yield of 68.7 to 78.2%.
[8] A lithium nitride particle produced by the method for producing a lithium nitride particle according to any one of [1] to [7 ].
[9] An apparatus for producing lithium nitride particles for carrying out the method for producing lithium nitride particles according to any one of [1] to [7], characterized by comprising a vacuum reduction furnace (1), a crucible (2), a vacuum pump (3), a micron ceramic filter (4), a flow control valve (5), a nitrogen gas supply device (6), and a reaction bin (7);
the nitrogen supply device (6) is communicated with a reaction bin (7), the nitrogen air inflow is adjusted through a flow control valve (5), and a heating unit is arranged in the reaction bin;
a vacuum pump (3) is arranged below the vacuum reduction furnace (1);
a crucible (2) is arranged at the center of the vacuum reduction furnace (1), and the crucible (2) adopts a resistance heating mode.
[10] The apparatus for preparing lithium nitride particles according to [9], wherein the vacuum reduction furnace is made of nickel-chromium alloy.
Compared with the prior art, the lithium raw material in the invention has wide sources, is not limited to the simple substance of metallic lithium, and greatly reduces the production cost of the lithium nitride particles; the method has the advantages that the metal lithium vapor is prepared by adopting a vacuum thermal reduction method, high-purity nitrogen is introduced to be mixed with the high-temperature metal lithium vapor, and a gas phase reaction is carried out to prepare the lithium nitride particles, so that the reaction rate is improved, the production efficiency is improved, the product quality is improved, the industrial production is facilitated, and the gas phase reaction is helpful for the nanocrystallization of the particle size of the lithium nitride particles; the unique formula of the hybrid auxiliary agent can promote the lithium raw material to be decomposed more fully on one hand, and is beneficial to the thermal reduction reaction on the other hand, so that the yield of the lithium nitride is higher.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of lithium nitride particles prepared in example 1;
FIG. 2 is an XRD pattern of lithium nitride particles prepared in example 1;
FIG. 3 is the XRD pattern of the hybrid adjuvant of example 1;
FIG. 4 is the XRD pattern of the hybrid adjuvant of example 2;
FIG. 5 is the XRD pattern of the hybrid additive of example 3;
FIG. 6 is the XRD pattern of the hybrid additive of example 4;
FIG. 7 is the XRD pattern of the hybrid adjuvant of example 5;
FIG. 8 is the XRD pattern of the hybrid adjuvant of example 6;
FIG. 9 is the XRD pattern of the hybrid adjuvant of example 7;
FIG. 10 is the XRD pattern of the hybrid adjuvant of example 8;
FIG. 11 is a schematic view of the apparatus of the present invention.
Detailed Description
In the present specification, when numerical ranges are used, they include both endpoints, and the units are common. For example, 1 to 20Pa means that the degree of vacuum is 1Pa or more and 20Pa or less.
The invention is described in further detail below with reference to the figures and specific embodiments.
The invention provides a process for preparing lithium nitride particles by taking a lithium-containing compound as a raw material and utilizing nitrogen and high-temperature metal lithium vapor to perform gas-phase chemical reaction under the vacuum condition, which specifically comprises the following steps:
step one, preparing the hybrid auxiliary agent
Calcium hydroxide and aluminum hydroxide are mixed according to the mass ratio (0.1-8.0): 1, preferably according to the mass ratio (0.152-7.775): 1, uniformly mixing by using a high-efficiency mixer (VCH-5), then increasing the temperature to 500-700 ℃ at the heating rate of 1-10 ℃/min under the vacuum degree of 1-20Pa, keeping the temperature for 2-4h, cooling to room temperature, and grinding a taken sample by using zirconium balls with the diameter of 5mm, wherein the ball material mass ratio is (10-15): 1, the rotating speed of the ball mill is 500-700r/min, the ball milling time is 1-3h, and the hybrid auxiliary agent xCaO-yAl is obtained after ball milling 2 O 3 Wherein x and y are mass fractions, continuously vacuumizing in the heating process, and discharging generated water vapor. The hybrid assistant xCaO-yAl is measured by a laser particle size analyzer 2 O 3 Particle diameter D50, hybrid assistant xCaO. YAl prepared 2 O 3 The particle diameter D50 of the particles is 10.0 μm or less, D50 or less 80.0 μm, preferably 10.0 μm or less, D50 or less 30.0 μm, more preferably 10.3 μm or less, D50 or less 29.5 μm. And (3) carrying out phase quantitative analysis on the hybrid auxiliary agent by using XRD (X-ray diffraction) test and GSAS (general-purpose chemical analysis) software so as to determine the values of x and y. By adjusting the ratio of calcium hydroxide to aluminum hydroxide, the heating rate, the holding time and the ball milling conditions as described above, the values of x and y may vary, but x and y are preferably 0.1. Ltoreq. X.ltoreq.0.9, 0.1. Ltoreq. Y.ltoreq.0.9, and x + y =1, as long as x and y satisfy 0 < x < 1, 0 < y < 1, and x + y =1; the beneficial effects of the hybrid additive of the present invention can be achieved.
The melting point of the lithium material is low, and when the lithium material is dissolved into a liquid state at a high temperature, the volatility of the lithium material is enhanced, and if a vacuum thermal decomposition process is adopted, the volatilization of the lithium material is more serious. Therefore, thisIn the invention, the addition of the hybridization auxiliary agent is beneficial to promoting the decomposition of the lithium raw material on one hand, and effectively inhibits the volatilization of the lithium raw material on the other hand, thereby remarkably improving the production yield. The mechanism of action of the hybrid assistant is as follows: the melting point of calcium oxide is up to 2580 ℃, and the calcium oxide can not melt in the process of decomposing the lithium raw material, plays the role of aggregate, locally forms a package, can prevent the melting and the loss of lithium raw material pellets, and further inhibits the volatilization of the lithium raw material. Secondly, the other important role of the calcium oxide is to form a stable compound with the oxide of the reducing agent in the vacuum thermal reduction process, thereby reducing the temperature of the reduction reaction and promoting the reduction process. The alumina can form a composite Li with lithium oxide which is a decomposition product of a lithium raw material 2 O·Al 2 O 3 The process lowers the pyrolysis reaction temperature and promotes thermal decomposition of the lithium raw material. By using both calcium oxide and aluminum oxide as the hybridization assistant, it is possible to suppress volatilization of the lithium raw material, lower the reduction reaction temperature, and promote thermal decomposition of the lithium raw material, on the one hand, and to more easily compact into blocks and grind. However, when calcium oxide is used alone as an auxiliary agent, the lithium raw material is not high in thermal decomposition rate and difficult to grind, although the lithium raw material easily forms a melt and volatilization of the lithium raw material is suppressed; however, when alumina is used alone as a hybridization assistant, it is difficult to compact the aluminum oxide into a lump with a lithium raw material, to suppress volatilization of the lithium raw material, to lower the reduction reaction temperature, and to reduce the utilization rate of the lithium raw material.
Step two, thermal decomposition of lithium raw material
Mixing the hybridization auxiliary agent and a lithium raw material (at least one of lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium peroxide and lithium nitrate, preferably lithium hydroxide or lithium carbonate or a mixture of the lithium hydroxide and the lithium carbonate) according to a mass ratio of (0.5-1.0): 1, preferably according to a mass ratio (0.75-0.95): 1, uniformly mixing by using a high-efficiency mixer (VCH-5), pressing into a briquette by using a sample inserting machine at the pressure of 30-100MPa, raising the temperature to 500-900 ℃ at the temperature rise rate of 1-10 ℃/min under the vacuum degree of 0.1-10Pa, keeping the temperature for 4-10h, and taking out the clinker after the reaction is finished. Ball-milling the clinker by adopting 5mm zirconium balls, wherein the mass ratio of the balls to the materials is (10-15): 1, the rotating speed of the ball mill is 500-700r/min, the ball milling time is 1-3h, and the grain diameter D50 of the ball-milled clinker is 10.0 mu m-45.0 mu m, preferably 10.0 mu m-20.0 mu m.
Step three, vacuum thermal reduction
Mixing clinker and a reducing agent according to the mass ratio of 1: (0.1-0.5), preferably 1: (0.2-0.3), uniformly mixing, pressing into lumps with the diameter of 20-30 mm and the mass of 40-80 g/lump by using a sample inserter at the pressure of 30-100MPa, raising the temperature to 700-1000 ℃ at the temperature raising rate of 1-10 ℃/min under the vacuum degree of 0.1-10Pa, preserving the heat for 4-8h, and carrying out vacuum thermal reduction in a vacuum reduction furnace to generate metal lithium vapor. The reducing agent is one or more than two of aluminum powder, silicon powder, iron powder, ferrosilicon, carbon powder, silicon aluminum powder, calcium carbide, ferrosilicon and magnesium powder, preferably aluminum powder, silicon powder and silicon aluminum powder.
It should be noted that the size and diameter of the briquette are not limited as long as the intended effect can be achieved, and it is preferable to prepare the briquette with a diameter of 20mm to 30mm and a mass of 40 to 80 g/briquette. By pressing the clinker and the reducing agent into the briquette, on one hand, a relatively stable proportion can be kept between the reaction raw materials so as to facilitate the thermal reduction reaction; on the other hand, the amount of dust carried in the lithium raw material can be reduced, and the quality of the product is improved. The calcium oxide and the aluminum oxide in the clinker form CaO & Li by reacting with the lithium oxide 2 O and Al 2 O 3 ·Li 2 And O, the melting point of the lithium oxide can be obviously reduced, so that the lithium oxide is in a molten state at a lower reduction temperature, and the state has a certain resistance, so that the crucible can generate enough heat.
Step four, synthesizing lithium nitride particles
The metallic lithium vapor in the third step firstly passes through a micron ceramic filter with the pore diameter of 1.0 mu m, and the dust in the metallic lithium vapor is effectively removed in the process; then, the metallic lithium vapor enters a reaction bin, and the reaction bin is heated to 300-500 ℃ through a heating unit; at the moment, a flow control valve of the nitrogen supply device is opened, the flow of nitrogen is controlled to be 0.10-0.60L/min, preferably 0.18-0.58L/min, nitrogen enters the reaction bin to fully contact with the high-temperature metal lithium vapor, and gas-phase reaction is carried out to generate lithium nitride particles. The nitrogen gas flow rate is not particularly limited as long as the supplied nitrogen gas can rapidly react with the lithium vapor, and it is preferable that the lithium vapor is in excess of the nitrogen gas in a stoichiometric molar ratio. After the reaction is finished, the equipment is cooled to room temperature, and then lithium nitride particles are collected in an argon atmosphere or a nitrogen atmosphere and packaged. Measuring the purity of the lithium nitride particles by using an ICP (inductively coupled plasma) tester, and analyzing the purity to be 99.0-99.4%; the yield of lithium nitride particles was calculated to be 68.7% -78.2% using the formula Z = I/Q = IM/(11.61 ma) × 100%; the particle diameter of the lithium nitride particles is 0.05 to 0.50. Mu.m, preferably 0.1 to 0.3. Mu.m, as determined by the laser particle size analyzer. This is the range of particle size that is difficult to produce by the current gas-liquid phase reaction process for preparing lithium nitride.
Compared with gas-liquid phase or gas-solid phase reaction, the gas-phase reaction is more sufficient, on one hand, the reaction rate is accelerated, the production efficiency is improved, and the industrial production is facilitated; on the other hand, the gas phase reaction contributes to the nanocrystallization of the lithium nitride particles, and the particle size of the lithium nitride particles is reduced.
In addition, the present invention provides an apparatus for producing lithium nitride particles for carrying out the method for producing lithium nitride particles according to claim 1, characterized in that the apparatus comprises: the device comprises a vacuum reduction furnace 1, a crucible 2, a vacuum pump 3, a micron ceramic filter 4, a flow control valve 5, a nitrogen supply device 6, a reaction bin 7 and the like; the nitrogen supply device 6 is communicated with a reaction bin 7, the nitrogen gas inflow is adjusted through a flow control valve 5, and a heating unit is arranged in the reaction bin;
a vacuum pump 3 is arranged below the vacuum reduction furnace 1;
a crucible 2 is arranged at the center of the vacuum reduction furnace 1, and the crucible 2 adopts a resistance heating mode.
Fig. 11 is a schematic view of the apparatus of the present invention, and the dimensions, configuration, positional relationship, etc. in the drawing are for illustrative purposes only and do not limit the present invention.
The raw materials, equipment, test conditions, detection methods, and the like used in the examples were as follows:
the lithium raw material is one or more than two of lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium peroxide and lithium nitrate, the quality purity is more than 99.0 percent, and the lithium raw material is purchased from Jiangxi Jianfeng lithium industry, inc.
The vacuum reduction furnace was purchased from Shanghai crystal precision instruments manufacturing Co., ltd for vacuum thermal reduction.
The three-temperature zone tube furnace is purchased from Shanghai Hanjun laboratory facilities, inc., and is used for preparing lithium nitride from lithium metal.
The XRD equipment manufacturer is Bruker (Bruker) in Germany, the model is Bruker D8, and XRD test conditions are as follows: the voltage is 40KV, the current is 40mA, the Cu target, the scanning range is 10-90 degrees, the step pitch is 0.02, and the scanning speed is 10 degrees/min, so that the method is used for qualitative and quantitative analysis of the hybridization auxiliary agent.
The laser particle size analyzer is purchased from Zhenhai physical optical instrument Co., ltd, and is LT3600, and is used for particle size testing of hybrid additives, clinker and lithium nitride.
The high-efficiency mixer (VCH-5) is purchased from Wuxi Taixian powder science and technology Limited company and is used for mixing powder materials in the production process.
The sample embedding machine is purchased from Yongan Xingheng mountain water prospecting mechanical Co., ltd, and is used for briquetting and forming powder.
The ICP detector is purchased from instrument gmbh of tassels, japan, and performs element component detection on the lithium nitride particles by a conventional method, that is, performs ICP test, and determines the purity of lithium nitride in the collected product.
The lithium nitride particle yield was calculated as follows:
weighing a lithium raw material with the mass M and the relative molecular mass M, wherein the chemical molecular formula of the lithium raw material contains a lithium atoms, and the theoretical yield of the lithium nitride is that the amount of the lithium atoms in the raw material is n = ma/M:
Q＝n/3×(6.941×3+14.007)＝11.61ma/M
the actual yield of lithium nitride in the product obtained after the end of the reaction is I, then: the yield of lithium nitride was Z = I/Q × 100% = IM/(11.61 ma) × 100%.
Example 1
Step one, preparing the hybrid auxiliary agent
Ca (OH) was mixed at room temperature with a high-performance mixer (VCH-5) 2 And Al (OH) 3 According to the mass ratio of 0.974:1, uniformly mixing, increasing the temperature to 600 ℃ at a heating rate of 5 ℃/min under the vacuum degree of 10Pa, keeping the temperature for 3h, cooling to room temperature, taking out, and grinding the taken-out sample by using a ball mill and a zirconium ball with the diameter of 5mm, wherein the ball material mass ratio is 12:1, the rotating speed of the ball mill is 600r/min, the ball milling time is 2 hours, and the hybrid additive is obtained after ball milling. The particle size D50 of the hybrid auxiliary agent is measured by a laser particle size analyzer, and the particle size D50 of the prepared hybrid auxiliary agent is 21.2 mu m. Performing phase quantitative analysis on the hybrid auxiliary agent by XRD test and GSAS software, wherein the hybrid auxiliary agent is 0.53CaO 0.47Al 2 O 3 。
As shown in FIG. 3, by XRD test, caO and Al are present in the hybrid additive 2 O 3 The phase of (1).
Step two, thermal decomposition of lithium raw material
At room temperature, using a high-efficiency mixer (VCH-5), mixing the hybridization auxiliary agent and lithium raw material lithium carbonate according to a mass ratio of 0.85:1, weighing 0.898kg of hybridization auxiliary agent and 1.056kg of lithium carbonate, uniformly mixing by using a powder mixer, pressing into a briquette by using a sample inserter at the pressure of 60MPa, then increasing the temperature to 700 ℃ at the heating rate of 5 ℃/min under the vacuum degree of 5Pa, carrying out thermal decomposition reaction, keeping the temperature for 8h, and taking out after the reaction is finished. And (3) ball-milling the taken materials by using a ball mill and zirconium balls with the diameter of 5mm, wherein the mass ratio of the balls to the materials is 12:1, the revolution of the ball mill is 600r/min, the ball milling time is 2 hours, clinker is obtained after ball milling, and the particle size D50 of the clinker is 15.6 microns by adopting a laser particle size analyzer.
Step three, vacuum thermal reduction
According to the mass ratio of clinker to reducer aluminum powder of 1:0.24, weighing 1.327kg of clinker, weighing 0.319kg of aluminum powder, uniformly mixing the clinker with a reducing agent, pressing the mixture into a briquette by using a sample embedding machine at the pressure of 80MPa, wherein the diameter of the briquette is about 20mm, the mass of each briquette is about 40g, raising the temperature of the briquette to the reduction temperature of 850 ℃ at the heating rate of 5 ℃/min under the vacuum degree of 5Pa in a crucible, preserving heat at 850 ℃ for 6h, and carrying out vacuum thermal reduction in a vacuum thermal reduction furnace to generate metal lithium vapor.
Step four, synthesizing lithium nitride particles
The metallic lithium vapor firstly passes through a micron ceramic filter with the pore diameter of 1.0 mu m, and the dust in the metallic lithium vapor is effectively removed in the process; then the metallic lithium vapor enters into a reaction bin, and the temperature of the reaction bin is set to be 400 ℃. At this time, a flow control valve on a nitrogen supply device is opened, the molar volume of the nitrogen is 22.4L/mol, the flow rate of the nitrogen is controlled to be 0.24L/min, and the nitrogen supply time corresponds to the heat preservation time in the vacuum thermal reduction step; the nitrogen gas flow rate is not particularly limited as long as the supplied nitrogen gas can rapidly react with the lithium vapor, and it is preferable that the lithium vapor is in excess of the nitrogen gas in a stoichiometric molar ratio. The purity of the nitrogen is 99.0-99.99%. And after the reaction is finished, the equipment is cooled to room temperature, then 255.66g of brownish red reaction product is collected under the nitrogen atmosphere, and the brownish red reaction product is subjected to vacuum packaging by using a heat sealing bag. Characterization tests were performed on lithium nitride particles, and fig. 1 is a Scanning Electron Microscope (SEM) image of lithium nitride particles prepared in example 1; FIG. 2 is an XRD pattern of the product of example 1, which is lithium nitride by comparison to a standard card.
Examples 1 to 8 use the apparatus shown in fig. 11, which is schematically illustrated in the form of a figure other than actual size and scale, and is not particularly limited as long as the intended effect can be achieved, and for example, the distance between the center of the crucible (2) and the micron ceramic filter (4) shown in fig. 11 may be 30 to 80cm.
The purity of the lithium nitride particles was measured using an ICP tester, and according to the analysis results of lithium element and nitrogen element, the purity of the lithium nitride particles prepared in example 1 was measured to be 99.2%, from which the actual yield I of the lithium nitride particles in the reaction product was calculated to be 253.61g;
the yield of lithium nitride particles was calculated using the formula Z = I/Q = IM/(11.61 ma) × 100%, and the yield of lithium nitride particles prepared in example 1 was found to be 76.4%;
the lithium nitride particles were milled and dispersed at 500rpm for 2 hours by a ball mill, and the particle diameter D50 of the lithium nitride particles was measured and analyzed by a laser particle size analyzer, and the particle diameter D50 was 0.22. Mu.m.
Examples 2 to 8
The steps of the preparation method are basically the same as in example 1, but are different in the relevant components, parameters and the like, and are specifically shown in tables 1 to 4.
Comparative examples 1 and 2
The steps of the preparation method are basically the same as in example 1, but are different in the relevant components, parameters and the like, and are specifically shown in tables 1 to 4.
Comparative example 3
Under the condition of room temperature and under the protection of nitrogen atmosphere, 5.0g of metal lithium is weighed in a glove box, the metal lithium is placed in a crucible and placed in a three-temperature-zone tubular furnace together, at the moment, nitrogen flow is introduced into the three-temperature-zone tubular furnace, and the nitrogen flow is 0.40L/min. Then, raising the temperature of the three-temperature-zone tube furnace to 350 ℃ at the heating rate of 5 ℃/min, preserving the heat for 8h, collecting 6.51g of dark red products under the nitrogen atmosphere, and calculating the actual yield of the lithium nitride to be 3.76g and the yield to be 45%; the lithium nitride particles were milled and dispersed at 500rpm for 2 hours by a ball mill, and the particle diameter D50 of the lithium nitride particles was measured and analyzed by a laser particle size analyzer, and the particle diameter D50 was 55.0. Mu.m.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
As shown in Table 4, when the test results of examples 1 to 8 and comparative examples 1 to 2 were analyzed, it was found that the hybrid assistant xCaO. YAl was more excellent than those of examples 1 to 8 2 O 3 In contrast, the assistants of comparative examples 1 to 2 were calcium oxide or aluminum oxide, respectively, which resulted in a low pyrolysis rate or a high volatilization rate of the lithium raw material, resulting in a significantly lower yield of lithium nitride particles than examples 1 to 8. In examples 1 to 8, the yield of lithium nitride particles was 68.7 to 78.2%, the purity was 99.0wt% or more, and the particle size was 0.05 to 0.50 μm, which is far superior to that of comparative examples 1 to 2, again indicating that the compound hybrid additive of the present invention significantly improves the decomposition rate and reduction rate of lithium raw materials.
The principle may be that the melting point of the lithium material is low, the volatility of the lithium material becomes strong when the lithium material is dissolved in a liquid state, and the volatilization of the lithium material becomes more serious by adopting a vacuum decomposition method. Therefore, in examples 1 to 8, a composite hybrid additive containing calcium oxide and aluminum oxide in a specific ratio range is used, and the addition of the hybrid additive is beneficial to promoting the decomposition of the lithium raw material, effectively inhibiting the volatilization of the lithium raw material, and improving the yield of the whole process. The melting point of calcium oxide is up to 2580 ℃, and the calcium oxide can not melt in the process of decomposing the lithium raw material, plays the role of aggregate, locally forms a package, can prevent the melting and the loss of lithium raw material pellets, and further inhibits the volatilization of the lithium raw material. Secondly, the other important role of the calcium oxide is to form a stable compound with the oxide of the reducing agent in the vacuum thermal reduction process, thereby reducing the temperature of the reduction reaction and promoting the reduction process. The alumina can form a compound Li with a decomposition product of a lithium raw material, lithium oxide 2 O·Al 2 O 3 The process lowers the pyrolysis reaction temperature and promotes thermal decomposition of the lithium raw material. The present invention uses both calcium oxide and aluminum oxide as a hybridization assistant, and thus, on the one hand, it is possible to suppress volatilization of a lithium raw material, reduce the reduction reaction temperature, and promote thermal decomposition of the lithium raw material, and on the other hand, it is easier to compact and grind into a lump. However alone makeWhen calcium oxide is used as an auxiliary agent, although the lithium raw material is easily melted and volatilization of the lithium raw material is remarkably inhibited, the thermal decomposition rate of the lithium raw material is not high and grinding is difficult, resulting in low yield of lithium nitride; however, when alumina is used alone as a hybridization promoter, al 2 O 3 It is difficult to form a block with the lithium raw material, to suppress volatilization of the lithium raw material, and to lower the reduction reaction temperature, resulting in a low utilization rate of the lithium raw material.
As shown in table 4, it can be seen from the analysis of the test results of examples 1 to 8 and comparative example 3 that the lithium nitride particles prepared by the gas phase reaction are superior to those prepared by the gas phase reaction in purity, particle size and yield, compared to the case of lithium nitride prepared by the solid lithium which is generally used in industry at present. The yield, purity and particle size of the lithium nitride particles prepared by the gas phase method of the invention have room for further improvement, but the invention has significant substantial progress compared with the prior art.
As can be seen from the analysis of the test results of comparative example 3, in comparative example 3, lithium nitride was prepared by introducing high-purity nitrogen gas into molten metal lithium, and the particle size of the prepared lithium nitride was much larger than that of the lithium nitrides prepared in examples 1 to 8 and comparative examples 1 to 2; the yield of lithium nitride was 45.0%, which is much lower than examples 1-8 and comparative examples 1-2, again indicating a higher production efficiency of lithium nitride particles prepared by gas phase reaction.
The beneficial effects of the invention are summarized as follows:
1. according to the invention, by precisely regulating and controlling the proportion of the hybrid auxiliary agent, the thermal reduction reaction temperature, the vacuum degree, the material, the reducing agent, the nitrogen flow and other conditions, the metallic lithium vapor prepared by the vacuum thermal reduction reaction can be directly used for carrying out gas phase reaction with high-purity nitrogen, so that the lithium vapor preparation and the lithium nitride particle preparation can be continuously carried out, and the production efficiency of the lithium nitride particle is improved. In addition, in terms of cost and raw materials, solid lithium is not used as a raw material, so that the production cost is greatly reduced, and the preparation process is simplified.
2. The composite hybrid additive is prepared by a method of sintering at 500-700 DEG CCan precisely regulate and control CaO and Al in the hybrid additive 2 O 3 The compounding ratio of (2) can promote the thermal decomposition reaction of the lithium raw material and promote the decomposition of the lithium raw material into lithium oxide. The melting point of the lithium raw material is low, and when the lithium raw material becomes a melt, the volatility thereof becomes strong. The hybrid additive plays a role of aggregate at high temperature, locally forms a package, prevents melting and loss of lithium raw material pellets, and thus plays a role in inhibiting volatilization of lithium raw materials; secondly, the hybrid assistant can form a compound Li with lithium oxide 2 O·Al 2 O 3 And Li 2 O & CaO can reduce the reaction temperature of vacuum thermal reduction, promote the reduction reaction and obviously improve the yield of lithium nitride particles.
3. Unlike the existing process in which nitrogen reacts with molten lithium metal to prepare lithium nitride, the present invention adopts gas phase reaction to react high purity nitrogen with vacuum heat reduced lithium metal vapor to prepare lithium nitride particle, and this makes the process reaction more complete, raises reaction rate and yield, and prepares lithium nitride particle with higher purity and smaller size. The gas phase reaction method of the invention successfully obtains the lithium nitride particles with the particle diameter of 0.05-0.50 mu m and the purity of more than 99 wt%.
The above description of all disclosed embodiments is merely illustrative of the best modes and techniques for carrying out the invention and is not intended to limit the invention. Those skilled in the art will understand and that various modifications to these embodiments will be readily apparent to those skilled in the art. It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments without departing from the spirit and scope of the invention, and these changes and modifications are to be included within the scope of the invention.
Description of the reference numerals
1. The device comprises a vacuum reduction furnace, 2, a crucible, 3, a vacuum pump, 4, a micron ceramic filter, 5, a flow control valve, 6, a nitrogen supply device, 7 and a reaction bin.
Claims (13)
1. A preparation method of lithium nitride particles is characterized by comprising the following steps:
(1) A step of preparing hybrid auxiliary agent, wherein calcium hydroxide and aluminum hydroxide are heated and then cooled, and ball milling is carried out to obtain the hybrid auxiliary agent with a chemical formula of xCaO-yAl 2 O 3 The hybrid additive of (1), wherein x and y are mass fractions, x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y =1;
(2) A step of thermal decomposition of a lithium raw material, wherein the hybrid auxiliary agent and the lithium raw material are uniformly mixed, pressed into a cluster under the pressure of 30-100MPa, heated to 500-900 ℃ at the heating rate of 1-10 ℃/min under the vacuum degree of 0.1-10Pa for thermal decomposition, the heat preservation time is 4-10h, and after the reaction is finished, ball milling is carried out to obtain clinker;
the mass ratio of the hybridization auxiliary agent to the lithium raw material is (0.5-1.0): 1; the lithium raw material is one or more than two of lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium peroxide and lithium nitrate;
(3) A vacuum thermal reduction step, wherein the clinker is uniformly mixed with a reducing agent and pressed into a briquette, and the briquette is subjected to vacuum thermal reduction in a vacuum reduction furnace to generate metal lithium vapor;
(4) A step of synthesizing lithium nitride particles, wherein the metal lithium vapor is introduced into a reaction bin, and nitrogen and the metal lithium vapor are in contact reaction to generate the lithium nitride particles;
the particle size of the lithium nitride particles is 0.05-0.50 mu m, and the purity is 99.0-99.4%.
2. The method of claim 1, wherein in the step (1), the calcium hydroxide and the aluminum hydroxide are uniformly mixed, the mixture is heated to 500-700 ℃ at a heating rate of 1-10 ℃/min under a vacuum degree of 1-20Pa, the temperature is kept for 2-4h, and after cooling, the mixture is ball-milled to obtain the hybrid assistant xCaO-yAl 2 O 3 Wherein x and y are 0.1-0.9, and x + y =1;
wherein the hybrid auxiliary agent xCaO yAl 2 O 3 The grain diameter D50 is more than or equal to 10.0 mu m and less than or equal to 80.0 mu m.
3. The method of claim 2, wherein the hybridization is performedAuxiliary agent xCaO yAl 2 O 3 The grain diameter D50 is more than or equal to 10.0 mu m and less than or equal to 30.0 mu m.
4. The method for preparing lithium nitride particles according to claim 1, wherein the particle size D50 of the clinker after ball milling in step (2) is 10.0 μm or less and D50 or less and 45.0 μm or less;
the mass ratio of the hybridization auxiliary agent to the lithium raw material is (0.75-0.95): 1.
5. the method for producing lithium nitride particles according to claim 4, wherein the particle diameter D50 of the ball-milled clinker is 10.0 μm or less and D50 or less and 20.0 μm or less.
6. The method for preparing lithium nitride particles according to claim 1, wherein in the step (3), the clinker is uniformly mixed with a reducing agent, the mixture is agglomerated at a pressure of 30-100MPa, the temperature is raised to 700-1000 ℃ at a heating rate of 1-10 ℃/min under a vacuum degree of 0.1-10Pa, the temperature is kept for 4-8h, and vacuum thermal reduction is performed in a vacuum reduction furnace to generate metallic lithium vapor;
wherein the diameter of the block mass is 20mm-30mm, and the mass is 40-80 g/block.
7. The method for preparing lithium nitride particles according to claim 1, wherein in the step (3), the reducing agent is one or more of aluminum powder, silicon powder, iron powder, ferrosilicon, carbon powder, silicoaluminum powder, calcium carbide, ferrosilicon, and magnesium powder;
wherein the mass ratio of the clinker to the reducing agent is 1: (0.1-0.5).
8. The method for preparing lithium nitride particles according to claim 7, wherein the reducing agent is aluminum powder, silicon powder or silico-aluminum powder, and the mass ratio of the clinker to the reducing agent is 1: (0.2-0.3).
9. The method for preparing lithium nitride particles according to claim 1, wherein in the step (4), the metallic lithium vapor enters a reaction bin, the flow rate of nitrogen is adjusted, nitrogen is fully contacted with the metallic lithium vapor to perform gas phase reaction, so as to generate lithium nitride particles, and the lithium nitride particles are packaged and sealed under inert gas;
wherein the nitrogen flow is 0.10-0.60L/min; the internal temperature of the reaction bin is 300-500 ℃, and the purity of the nitrogen is 99.0-99.99%; the inert gas is nitrogen or argon.
10. The method for preparing lithium nitride particles according to claim 9, wherein the nitrogen flow rate is 0.18 to 0.58L/min.
11. The method for producing lithium nitride particles according to claim 1, wherein the particle diameter of the lithium nitride particles is 0.10 to 0.30 μm.
12. An apparatus for producing lithium nitride particles for carrying out the method for producing lithium nitride particles according to any one of claims 1 to 11, characterized in that the apparatus comprises a vacuum reduction furnace (1), a crucible (2), a vacuum pump (3), a micron ceramic filter (4), a flow control valve (5), a nitrogen gas supply device (6), a reaction bin (7);
the nitrogen supply device (6) is communicated with a reaction bin (7), the nitrogen air inflow is adjusted through a flow control valve (5), and a heating unit is arranged in the reaction bin;
a vacuum pump (3) is arranged below the vacuum reduction furnace (1);
a crucible (2) is arranged at the center of the vacuum reduction furnace (1), and the crucible (2) adopts a resistance heating mode.
13. The apparatus for preparing lithium nitride particles according to claim 12, wherein the vacuum reduction furnace is made of nichrome.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011616707.7A CN113526474B (en) | 2020-12-31 | 2020-12-31 | Lithium nitride particles, and method and apparatus for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011616707.7A CN113526474B (en) | 2020-12-31 | 2020-12-31 | Lithium nitride particles, and method and apparatus for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113526474A CN113526474A (en) | 2021-10-22 |
| CN113526474B true CN113526474B (en) | 2023-03-31 |
Family
ID=78094316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011616707.7A Active CN113526474B (en) | 2020-12-31 | 2020-12-31 | Lithium nitride particles, and method and apparatus for producing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113526474B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114515820A (en) * | 2022-01-27 | 2022-05-20 | 安徽千鑫通讯科技有限公司 | Production process of high-strength anti-falling mobile phone shell |
| CN115312771A (en) * | 2022-03-10 | 2022-11-08 | 深圳市德方创域新能源科技有限公司 | Lithium supplement additive and preparation method and application thereof |
| CN116216652A (en) * | 2023-01-17 | 2023-06-06 | 北京恩力动力技术有限公司 | Preparation method of lithium sulfide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125211A (en) * | 1995-09-07 | 1996-06-26 | 华东理工大学 | Large block body tight nanometer ceramic material and its preparation method |
| CN103606660A (en) * | 2013-11-06 | 2014-02-26 | 中国科学院化学研究所 | Alumina-coated granules, as well as preparation method and application thereof |
| CN106450229A (en) * | 2016-11-22 | 2017-02-22 | 深圳市鑫永丰科技有限公司 | Lithium metal powder coated by conductive polymer and preparation method and device of lithium metal powder |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4321163A (en) * | 1978-11-21 | 1982-03-23 | Max-Planck-Gesellschaft | Lithium nitride of increased conductivity, method for its preparation, and its use |
| JPS60189170A (en) * | 1984-03-06 | 1985-09-26 | Sanyo Electric Co Ltd | Solid electrolyte battery |
| JP2001048504A (en) * | 1999-07-29 | 2001-02-20 | Nippon Soda Co Ltd | Production of lithium nitride |
| CN1258239C (en) * | 2003-05-19 | 2006-05-31 | 中国科学院青海盐湖研究所 | Method for producing lithium ion cell negative electrode material |
| CN1213158C (en) * | 2003-07-02 | 2005-08-03 | 黄启新 | Lithium preparing process with lithium carbonate |
| CN101456750A (en) * | 2008-12-23 | 2009-06-17 | 大连海事大学 | Lithium nitride/ceramic base composite material with high activity lithiation/delithiation performance |
| CN101642815A (en) * | 2009-09-04 | 2010-02-10 | 黄启新 | Method for preparing metal lithium at high temperature employing the electrical conductivity of molten slag |
| CN101818265A (en) * | 2010-03-25 | 2010-09-01 | 黄启新 | Method for preparing metallic lithium by using lithium hydroxide |
| CN102560148B (en) * | 2012-01-19 | 2014-05-21 | 东北大学 | Method for smelting lithium by vacuum aluminothermic reduction |
| CN111224077B (en) * | 2018-11-27 | 2021-06-11 | 中国科学院大连化学物理研究所 | Lithium nitride composite material and preparation and application thereof |
| CN211601529U (en) * | 2019-11-27 | 2020-09-29 | 天津炜润达新材料科技有限公司 | Vacuum sintering furnace is used in silicon nitride production |
| CN111057850B (en) * | 2020-01-03 | 2020-12-25 | 四川万邦胜辉新能源科技有限公司 | Method for preparing high-purity lithium metal by vacuum thermal reduction method |
| CN111187924B (en) * | 2020-03-06 | 2024-04-12 | 北京欧菲金太科技有限责任公司 | Continuous lithium smelting device and method for lithium-containing material |
| CN111952517A (en) * | 2020-08-26 | 2020-11-17 | 复阳固态储能科技(溧阳)有限公司 | Diaphragm containing lithium nitride thin film layer and preparation method and application thereof |
-
2020
- 2020-12-31 CN CN202011616707.7A patent/CN113526474B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125211A (en) * | 1995-09-07 | 1996-06-26 | 华东理工大学 | Large block body tight nanometer ceramic material and its preparation method |
| CN103606660A (en) * | 2013-11-06 | 2014-02-26 | 中国科学院化学研究所 | Alumina-coated granules, as well as preparation method and application thereof |
| CN106450229A (en) * | 2016-11-22 | 2017-02-22 | 深圳市鑫永丰科技有限公司 | Lithium metal powder coated by conductive polymer and preparation method and device of lithium metal powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113526474A (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113526474B (en) | Lithium nitride particles, and method and apparatus for producing same | |
| CN113816379B (en) | Preparation method of nano hafnium boride powder | |
| Wu et al. | Preparation and purification of titanium carbide via vacuum carbothermic reduction of ilmenite | |
| CN101863663B (en) | Combustion method for preparing submicron grade titanium carbide polycrystal powder | |
| JP2012155916A (en) | Lithium secondary battery cathode active material and its manufacturing method, and precursor of the same and its manufacturing method | |
| CN109912309B (en) | Novel mixing process for preparing aluminum nitride powder | |
| CN101786624B (en) | Method for preparing superfine boron carbide powder by using combustion method | |
| Xuan et al. | Rapid hydrogen generation from the reaction of aluminum/activated charcoal composite with alkaline solution | |
| JP2013199402A (en) | Method for producing silicon | |
| CN113184870A (en) | Macro-particle-size-controllable LaB6Method for preparing powder | |
| US20240011124A1 (en) | Method and device for preparing ultrathin metal lithium foil | |
| Parascos et al. | Compositional and structural control in LLZO solid electrolytes | |
| Bai et al. | Optimization and mechanism in preparing active magnesium oxide from magnesite | |
| JP7461341B2 (en) | Brownmillerite-based polycrystalline melt products | |
| Fi̇gen et al. | Mechanism for formation of NaBH 4 proposed as low-pressure process for storing hydrogen in borosilicate glass–sodium solid system: a hydrogen storage material | |
| CN111362275B (en) | Preparation method of lithium borate | |
| Ma et al. | Analysis of KF behavior and inverse reaction molecular kinetics simulation in the vacuum carbothermic reduction of magnesium oxide | |
| CN102332566A (en) | Low-sodium and low-potassium lithium manganate material for lithium ion battery anode and preparation method for lithium manganate material | |
| Lan et al. | Synthesis of Sub-micron Spherical α-Si 3 N 4 Powder by Direct Nitridation of Silicon Saw Dust | |
| CN110563339A (en) | Preparation method of anhydrous lithium borate fluxing agent | |
| Akkoyunlu et al. | Synthesis of Submicron‐Size CaB6 Powders using Various Boron Sources | |
| KR102509062B1 (en) | Mass producing method of Lithium sulfide | |
| CN115925428B (en) | Hexagonal boron nitride powder and preparation method and application thereof | |
| CN111646504B (en) | Nano lanthanum zirconate and preparation method thereof | |
| RU2734692C1 (en) | Method of producing fuel compositions based on uranium dioxide with the addition of a burnable neutron absorber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |