CN116262955B - Lithium tin intermetallic compound and preparation method and application thereof - Google Patents
Lithium tin intermetallic compound and preparation method and application thereof Download PDFInfo
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- CN116262955B CN116262955B CN202111534787.6A CN202111534787A CN116262955B CN 116262955 B CN116262955 B CN 116262955B CN 202111534787 A CN202111534787 A CN 202111534787A CN 116262955 B CN116262955 B CN 116262955B
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- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 72
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 70
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000000956 alloy Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 239000013081 microcrystal Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 6
- 229910001128 Sn alloy Inorganic materials 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 description 44
- 238000003723 Smelting Methods 0.000 description 14
- 239000002131 composite material Substances 0.000 description 6
- 229910008365 Li-Sn Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910006759 Li—Sn Inorganic materials 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910011205 Li7Sn2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910008015 Li-M Inorganic materials 0.000 description 1
- 229910007600 Li2Sn5 Inorganic materials 0.000 description 1
- 229910010766 Li5Sn2 Inorganic materials 0.000 description 1
- 229910011217 Li7Sn3 Inorganic materials 0.000 description 1
- 229910012381 LiSn Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium tin intermetallic compound, a preparation method and application thereof, and belongs to the technical field of lithium battery materials. The lithium tin intermetallic compound is Li 22Sn5, and the preparation method comprises the following steps: a. under the protection of inert gas, respectively raising the temperature of metallic lithium and metallic tin to 400-450 ℃, preserving heat and stirring for 10-15 min to respectively obtain tin liquid and lithium liquid; b. and d, mixing the tin liquid and the lithium liquid in the step a, wherein the tiny crystal grains generated on the container wall are Li 22Sn5. The preparation method of the lithium tin intermetallic compound Li 22Sn5 has safer process, simple operation and easy control, is suitable for industrial popularization, has less energy consumption and good economic benefit, and the prepared lithium tin alloy has wide intermediate application range.
Description
Technical Field
The invention relates to a lithium-tin intermetallic compound Li 22Sn5, a preparation method and application thereof, belonging to the technical field of lithium battery materials.
Background
In recent years, due to urgent demands of next-generation high-specific-energy lithium ion batteries, lithium-containing anode materials Li-M (elements undergoing alloying reaction with Li) based on an alloy reaction mechanism are receiving more and more attention as a class of lithium ion battery anode materials with great potential. The metal tin has the characteristics of relatively low melting point, low cost, good conductivity and the like, and the Li-Sn alloy formed by the metal tin and lithium becomes a cathode material with great advantages, and the metal tin is characterized by high specific capacity and low overpotential. During the preparation process, lithium and tin typically form various intermetallic compounds such as Li 22Sn5、Li7Sn3、Li7Sn2、Li2Sn5, liSn, etc., wherein: due to the inherent metallic property and good conductivity of Sn, the Li 22Sn5 alloy is guaranteed to have good battery performance at a higher rate, and the Li 22Sn5 alloy serving as a negative electrode has the advantages of being far higher than the specific capacity of graphite, high initial coulombic efficiency and the like, and is taken as an important research object at one time.
At present, the preparation research on specific lithium-tin intermetallic compounds is less, and most Li-Sn alloy preparation methods only stay in an experimental stage, cannot be produced in a large scale, and limit the realization of industrial application. Zhang, chen, xinlong, et al .Roll-to-roll prelithiation of Sn foil anode suppresses gassing and enables stable full-cell cycling of lithium ion batteries. and CN111952545a disclose the preparation of Li-Sn alloys by mechanical rolling for lithium battery negative electrode prelithiation ;Lou J,Chen K,Yang N,et al.Improved Cycle Stability of LiSn Alloy Anode for Different Electrolyte Systems in Lithium Battery[J].Nanomaterials,2021,11(2):300., disclosing an atomic ratio of 49:1, after being heated to a molten state, the lithium tin metal is uniformly mixed to form a lithium tin alloy, and is used as a lithium battery anode material, three intermediate phases of Li 22Sn5、Li7Sn2、Li5Sn2 are formed through XRD analysis and detection, the smelting temperature and the smelting time are not indicated in the article, and the amount of the generated Li 22Sn5 is very small. Gao J, chen C, dong Q, et al, stamping Flexible Li Alloy Anodes [ J ]. ADVANCED MATERIALS,2021 discloses that a certain proportion of lithium is mixed with tin, and after being melted at high temperature to form molten lithium tin alloy, the molten lithium tin alloy is attached to a Cu foil in a printing mode to be used as a lithium ion battery cathode composite material. Patent CN111313013 a presses a tin foil with a lithium ribbon through a pressing device to form a lithium tin alloy, and prepares lithium tin alloy powder for negative electrode lithium supplement through a grinding device. However, none of the above methods discloses how to prepare Li 22Sn5.
High-temperature smelting is a more conventional means for lithium alloying, however, in the smelting process, the minimum temperature of Li-Sn forming intermetallic compound Li 22Sn5 is 783 ℃, and the problems of safety, economic benefit and the like are brought to the preparation of the lithium tin alloy due to the activity of lithium, the corrosiveness of lithium liquid to equipment at high temperature and the difficult controllability of preparation conditions.
Disclosure of Invention
A first object of the present invention is to provide a novel method for preparing lithium tin intermetallic compound Li 22Sn5.
To achieve the first object of the present invention, the lithium tin intermetallic compound is Li 22Sn5, and the preparation method comprises:
a. In an inert gas environment, respectively raising the temperature of the metal lithium and the metal tin to 400-450 ℃, and stirring for 10-15 min after the metal lithium is melted to respectively obtain tin liquid and lithium liquid;
b. And d, mixing the tin liquid and the lithium liquid in the step a, wherein the tiny crystal grains generated on the container wall are Li 22Sn5.
The inert atmosphere may be a gas that does not react with lithium, tin, such as argon.
In a specific embodiment, the whole experimental environment of the steps a and b is in a drying room with dew point not higher than-50 ℃.
In a specific embodiment, the Li mass fraction of the metallic lithium in the step a is more than 99.95%; the mass fraction of the metal tin is more than 99.99%.
In one embodiment, the temperature of the whole reaction process after mixing in the step b is maintained at 400-450 ℃.
In a specific embodiment, the tin liquid in the step b is 40-80 wt% and the rest is lithium liquid; more preferably, the tin liquor is 60-80 wt%.
In a specific embodiment, the step b further comprises stirring, and the rotating speed of stirring in the step a and the step b is 100-200 r/min.
In one embodiment, the stirring time in step b=5 min+ [ (tin liquor mass% 40 wt%)/5 wt% ] min.
In one embodiment, the method further comprises: c. and after no micro crystal grains are formed on the wall, reducing the temperature to 190-220 ℃, casting out redundant metal liquid, closing stirring, and taking out the micro crystal grains in the container to obtain Li 22Sn5.
In one embodiment, the method further comprises d. Milling and classifying the fine grains into Li 22Sn5 alloy powder in an environment having a dew point of not higher than-50 ℃; the particle size of the Li 22Sn5 alloy powder is preferably not more than 100 μm.
In one embodiment, the Li 22Sn5 alloy powder has a purity of 99.20 to 99.85%.
The second object of the present invention is to provide a lithium tin intermetallic compound Li 22Sn5, wherein the lithium tin intermetallic compound Li 22Sn5 is prepared by the method, and the purity is 99.20-99.85%; preferably, the particle size of the lithium tin intermetallic compound Li 22Sn5 is not more than 100 μm.
The third purpose of the invention is to provide the lithium tin intermetallic compound Li 22Sn5 prepared by the method or the application of the lithium tin intermetallic compound Li 22Sn5 in the preparation of a negative electrode material of a lithium battery, a composite material and solid electrolyte addition or micro-nano particles.
The beneficial effects are that:
According to the preparation method of the lithium tin intermetallic compound Li 22Sn5, the heat released by metal bond formation during smelting and synthesizing the intermetallic compound Li 22Sn5 is generated by utilizing lithium tin, so that more lithium and tin are generated. The smelting temperature is controlled to be 450 ℃ at the highest, so that the experimental safety, the equipment maintenance cost, the income and the like are improved. The lithium tin intermetallic compound Li 22Sn5 is mainly applied to the aspects of lithium battery cathode materials, preparation of composite materials, solid electrolyte addition, micro-nano particles and the like.
The specific advantages are as follows:
(1) Safety: the higher the activity of lithium metal, the higher the smelting temperature, the greater the safety risk, and the temperature is controlled below 450 ℃, so that the smelting process is safer.
(2) The process is as follows: the whole smelting, stirring and alloy treatment processes are simple to operate, easy to control and suitable for industrial popularization.
(3) The economic benefit is as follows: because the preparation temperature is lower, the electric energy consumption can be reduced, excessive metal steam can not be generated, the corrosiveness to the smelting container is lower, and the equipment maintenance cost is further reduced; the prepared lithium tin alloy intermediate phase has very wide application and is mainly characterized in that: the method is used for preparing ternary or multi-element lithium-based alloy raw materials by a solid phase reaction method. Secondly, the lithium content of the lithium-containing composite material is high in mass percentage, and the lithium-containing composite material can be developed for pre-lithiated powder cores.
Drawings
FIG. 1 is an XRD pattern for the lithium tin alloy powder of example 1;
Fig. 2 is a secondary electron diagram of the lithium tin alloy powder of example 1.
Detailed Description
To achieve the first object of the present invention, the lithium tin intermetallic compound is Li 22Sn5, and the preparation method comprises:
a. In an inert gas environment, respectively raising the temperature of the metal lithium and the metal tin to 400-450 ℃, and stirring for 10-15 min after the metal lithium is melted to respectively obtain tin liquid and lithium liquid;
b. And d, mixing the tin liquid and the lithium liquid in the step a, wherein the tiny crystal grains generated on the container wall are Li 22Sn5.
In a specific embodiment, the whole experimental environment of the steps a and b is in a drying room with dew point not higher than-50 ℃.
In a specific embodiment, the Li mass fraction of the metallic lithium in the step a is more than 99.95%; the mass fraction of the metal tin is more than 99.99%.
In one embodiment, the temperature of the whole reaction process after mixing in the step b is maintained at 400-450 ℃.
In a specific embodiment, the tin liquid in the step b is 40-80 wt% and the rest is lithium liquid; more preferably, the tin liquor is 60-80 wt%.
In a specific embodiment, the step b further comprises stirring, and the rotating speed of stirring in the step a and the step b is 100-200 r/min.
In one embodiment, the stirring time in step b=5 min+ [ (tin liquor mass% 40 wt%)/5 wt% ] min.
In one embodiment, the method further comprises: c. and after no micro crystal grains are formed on the wall, reducing the temperature to 190-220 ℃, casting out redundant metal liquid, closing stirring, and taking out the micro crystal grains in the container to obtain Li 22Sn5.
In one embodiment, the method further comprises d. Milling and classifying the fine grains into Li 22Sn5 alloy powder in an environment having a dew point of not higher than-50 ℃; the particle size of the Li 22Sn5 alloy powder is preferably not more than 100 μm.
In one embodiment, the Li 22Sn5 alloy powder has a purity of 99.20 to 99.85%.
The second object of the present invention is to provide a lithium tin intermetallic compound Li 22Sn5, wherein the lithium tin intermetallic compound Li 22Sn5 is prepared by the method, and the purity is 99.20-99.85%; preferably, the particle size of the lithium tin intermetallic compound Li 22Sn5 is not more than 100 μm.
The third purpose of the invention is to provide the lithium tin intermetallic compound Li 22Sn5 prepared by the method or the application of the lithium tin intermetallic compound Li 22Sn5 in the preparation of a negative electrode material of a lithium battery, a composite material and solid electrolyte addition or micro-nano particles.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
A preparation method of a lithium tin intermetallic compound Li 22Sn5 comprises the following steps of calculating the total mass of lithium and tin to be 100 g. The method comprises the following steps:
(1) Under the inert atmosphere environment, weighing 20g of lithium and 80g of tin, respectively placing the lithium and the 80g of tin into two smelting containers, heating to 400 ℃ to melt, starting a mechanical stirring device after the two metals are melted, keeping the rotating speed at 100r/min, and stirring for 15min. Wherein: the metal lithium is battery grade lithium ingot (mass fraction 99.95%), and the metal tin (mass fraction 99.99%) is tin particles.
(2) Pouring molten tin into lithium liquid, instantaneously generating a plurality of micro grains on the container wall, keeping the temperature of the mixed liquid at 400 ℃, continuously stirring the metal mixed liquid for 13min, reducing the temperature to 200 ℃ after the micro grains are not regenerated on the wall, casting out redundant metal lithium liquid, closing stirring, and taking out solid substances in the container, namely Li 22Sn5
(3) In the environment with dew point not higher than-50 deg.c, the alloy powder with purity below 80 microns and 99.52% is produced through grinding.
As can be seen from fig. 1 and 2, when the graphs are combined, the intermetallic compound mainly generated by Li and Sn is Li 22Sn5, other impurity phases are not generated basically, and the crystal grain cleavage plane is obviously ordered under high multiple.
Example 2
A preparation method of a lithium tin intermetallic compound Li 22Sn5 comprises the following steps of calculating the total mass of lithium and tin to be 100 g. The method comprises the following steps:
(1) Under the inert atmosphere environment, 40g of lithium and 60g of tin are weighed and respectively placed in two smelting containers, the temperature is raised to 400 ℃ to melt, and after the two metals are melted, a mechanical stirring device is started to keep the rotating speed at 100r/min, and stirring is carried out for 10min. Wherein: the metal lithium is battery grade lithium ingot (mass fraction 99.95%), and the metal tin (mass fraction 99.99%) is tin particles.
(2) Pouring molten tin into lithium liquid, instantaneously generating a plurality of micro grains on the container wall, keeping the temperature of the mixed liquid at 400 ℃, continuously stirring the metal mixed liquid for 9min, reducing the temperature to 200 ℃ after the micro grains are not regenerated on the wall, casting out redundant metal lithium liquid, closing stirring, and taking out solid substances in the container, namely Li 22Sn5
(3) In the environment with dew point not higher than-50 deg.c, the alloy powder with purity below 80 microns and 99.48% is produced through grinding.
Example 3
A preparation method of a lithium tin intermetallic compound Li 22Sn5 comprises the following steps of calculating the total mass of lithium and tin to be 100 g. The method comprises the following steps:
(1) Under the inert atmosphere environment, 60g of lithium and 40g of tin are weighed and respectively placed in two smelting containers, the temperature is raised to 400 ℃ to melt, and after the two metals are melted, a mechanical stirring device is started to keep the rotating speed at 100r/min, and stirring is carried out for 12min. Wherein: the metal lithium is battery grade lithium ingot (mass fraction 99.95%), and the metal tin (mass fraction 99.99%) is tin particles.
(2) Pouring molten tin into lithium liquid, instantaneously generating a plurality of micro grains on the container wall, keeping the temperature of the mixed liquid at 400 ℃, continuously stirring the metal mixed liquid for 5min, reducing the temperature to 200 ℃ after the micro grains are not regenerated on the wall, casting out redundant metal lithium liquid, closing stirring, and taking out solid substances in the container, namely Li 22Sn5
(3) In the environment with dew point not higher than-50 deg.c, the alloy powder with purity below 80 microns and 99.42% is produced through grinding in grinding apparatus.
Example 4
A preparation method of a lithium tin intermetallic compound Li 22Sn5 comprises the following steps of calculating the total mass of lithium and tin to be 100 g. The method comprises the following steps:
(1) Under the inert atmosphere environment, weighing 20g of lithium and 80g of tin, respectively placing the lithium and the 80g of tin into two smelting containers, heating to 450 ℃ to melt, starting a mechanical stirring device after the two metals are melted, keeping the rotating speed at 120r/min, and stirring for 15min. Wherein: the metal lithium is battery grade lithium ingot (mass fraction 99.95%), and the metal tin (mass fraction 99.99%) is tin particles.
(2) Pouring molten tin into lithium liquid, instantaneously generating a plurality of tiny grains on the wall of the container, keeping the temperature of the mixed liquid at 450 ℃, continuously stirring the mixed liquid for 13min, reducing the temperature to 200 ℃ after the tiny grains are not regenerated on the wall, casting out redundant lithium liquid, closing stirring, and taking out solid substances in the container, namely Li 22Sn5.
(3) In the environment with dew point not higher than-50 deg.c, the alloy powder with purity below 60 microns and 99.72% is produced through grinding in grinding apparatus.
Claims (10)
1. The preparation method of the lithium tin intermetallic compound is characterized in that the lithium tin intermetallic compound is Li 22Sn5, and comprises the following steps:
a. In an inert gas environment, respectively raising the temperature of the metal lithium and the metal tin to 400-450 ℃, and stirring for 10-15 min after the metal lithium is melted to respectively obtain tin liquid and lithium liquid;
b. Mixing the tin liquid and the lithium liquid in the step a, wherein the tiny crystal grains generated on the container wall are Li 22Sn5;
the method further comprises the steps of: c. and after no micro crystal grains are formed on the wall, reducing the temperature to 190-220 ℃, casting out redundant metal liquid, closing stirring, and taking out the micro crystal grains in the container to obtain Li 22Sn5.
2. The method for preparing lithium tin intermetallic compound according to claim 1, wherein the whole experimental environment of the steps a and b is in a drying room with dew point not higher than-50 ℃.
3. The method for producing a lithium tin intermetallic compound according to claim 1 or 2, wherein the Li mass fraction of the metallic lithium in the step a is 99.95% or more; the mass fraction of the metal tin is more than 99.99%.
4. The method for preparing a lithium tin intermetallic compound according to claim 1 or 2, wherein the temperature of the whole reaction process after the mixing in the step b is maintained at 400 to 450 ℃.
5. The method for producing a lithium tin intermetallic compound according to claim 1 or 2, wherein the tin liquid in the step b is 40 to 80wt% with the remainder being lithium liquid; more preferably, the tin liquor is 60-80 wt%.
6. The method for preparing a lithium tin intermetallic compound according to claim 1 or 2, wherein the step b further comprises stirring, and the stirring speed in the step a and the step b is 100-200 r/min.
7. The method for producing a lithium tin intermetallic compound according to claim 6, wherein the stirring time in the step b=5 min+ [ (mass% of tin solution-40 wt%)/5 wt% ] min.
8. The method for producing a lithium tin intermetallic compound according to claim 1 or 2, further comprising d. grinding and classifying the fine crystal grains into Li 22Sn5 alloy powder in an environment having a dew point of not higher than-50 ℃.
9. The method for producing a lithium-tin intermetallic compound according to claim 8, wherein the particle size of the Li 22Sn5 alloy powder is not more than 100 μm.
10. The method for producing a lithium tin intermetallic compound according to claim 9, wherein the purity of the Li 22Sn5 alloy powder is 99.20 to 99.85%.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0867955A1 (en) * | 1997-03-26 | 1998-09-30 | Seiko Instruments Inc. | Non-aqueous electrolyte secondary battery |
| US5998064A (en) * | 1996-10-25 | 1999-12-07 | Japan Storage Battery Co., Ltd. | Negative active material for lithium secondary battery and producing method thereof |
| CN1688044A (en) * | 2005-05-08 | 2005-10-26 | 北京科技大学 | Method of preparing Sn-Sb alloy material for negative electrode of lithium ion cell |
| CN102031432A (en) * | 2010-12-22 | 2011-04-27 | 重庆市科学技术研究院 | Sn-containing fine-grained magnesium-lithium tin alloy |
| WO2012174235A1 (en) * | 2011-06-14 | 2012-12-20 | Brookhaven Science Associates, Llc | INTERMETALLIC M-Sn5 (M=Fe, Cu, Co, Ni) COMPOUND AND A METHOD OF SYNTHESIS THEREOF |
| CN109904417A (en) * | 2019-01-29 | 2019-06-18 | 电子科技大学 | A lithium-dissimilar metal composite negative electrode material and preparation method thereof |
| CN110998920A (en) * | 2017-08-15 | 2020-04-10 | 魁北克电力公司 | Electrode material in the form of a lithium-based alloy and method for producing same |
| CN111455410A (en) * | 2020-02-28 | 2020-07-28 | 东南大学 | A method for preparing lithium tin alloy nanocrystals by electron beam irradiation |
| CN112813325A (en) * | 2020-12-30 | 2021-05-18 | 山东重山光电材料股份有限公司 | Lithium-silicon-tin alloy material and preparation method and application thereof |
| CN113782733A (en) * | 2021-11-09 | 2021-12-10 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | A negative electrode material for solid-state lithium battery and its application |
| CN116262955A (en) * | 2021-12-15 | 2023-06-16 | 重庆天齐锂业有限责任公司 | Lithium tin intermetallic compound and preparation method and application thereof |
Family Cites Families (2)
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| US11217788B2 (en) * | 2019-04-16 | 2022-01-04 | Board Of Trustees Of Northern Illinois University | Doped lithium anode, battery having a doped lithium anode, and methods of use thereof |
-
2021
- 2021-12-15 CN CN202111534787.6A patent/CN116262955B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998064A (en) * | 1996-10-25 | 1999-12-07 | Japan Storage Battery Co., Ltd. | Negative active material for lithium secondary battery and producing method thereof |
| EP0867955A1 (en) * | 1997-03-26 | 1998-09-30 | Seiko Instruments Inc. | Non-aqueous electrolyte secondary battery |
| CN1688044A (en) * | 2005-05-08 | 2005-10-26 | 北京科技大学 | Method of preparing Sn-Sb alloy material for negative electrode of lithium ion cell |
| CN102031432A (en) * | 2010-12-22 | 2011-04-27 | 重庆市科学技术研究院 | Sn-containing fine-grained magnesium-lithium tin alloy |
| WO2012174235A1 (en) * | 2011-06-14 | 2012-12-20 | Brookhaven Science Associates, Llc | INTERMETALLIC M-Sn5 (M=Fe, Cu, Co, Ni) COMPOUND AND A METHOD OF SYNTHESIS THEREOF |
| CN110998920A (en) * | 2017-08-15 | 2020-04-10 | 魁北克电力公司 | Electrode material in the form of a lithium-based alloy and method for producing same |
| CN109904417A (en) * | 2019-01-29 | 2019-06-18 | 电子科技大学 | A lithium-dissimilar metal composite negative electrode material and preparation method thereof |
| CN111455410A (en) * | 2020-02-28 | 2020-07-28 | 东南大学 | A method for preparing lithium tin alloy nanocrystals by electron beam irradiation |
| CN112813325A (en) * | 2020-12-30 | 2021-05-18 | 山东重山光电材料股份有限公司 | Lithium-silicon-tin alloy material and preparation method and application thereof |
| CN113782733A (en) * | 2021-11-09 | 2021-12-10 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | A negative electrode material for solid-state lithium battery and its application |
| CN116262955A (en) * | 2021-12-15 | 2023-06-16 | 重庆天齐锂业有限责任公司 | Lithium tin intermetallic compound and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Mossbauer spectra as a"fingerprint"in tin–lithium compounds: Applications to Li-ion batteries;F.Robert et al.，;《Journal of Solid State Chemistry》;20061106;第180卷;340 * |
| 液态锂锡合金表面张力的初步研究;谢波;翁葵平;;材料导报;20111125(22);全文 * |
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