CN110767884A - Inert metal lithium powder with core-shell structure - Google Patents
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 168
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000000843 powder Substances 0.000 title claims abstract description 125
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 239000011258 core-shell material Substances 0.000 title claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 229920000767 polyaniline Polymers 0.000 claims description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 12
- 239000013589 supplement Substances 0.000 description 6
- 238000000889 atomisation Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an inert metal lithium powder with a core-shell structure, and belongs to the technical field of lithium battery manufacturing. According to the invention, active metal lithium is prepared into powder of 5-100 um, and one or more layers of inert brittle materials are coated on the surface of the prepared metal lithium powder, so that the prepared inert metal lithium powder does not react in air at the temperature of below 90 ℃, NMP solvent or other reagents containing a small amount of water, and has good stability. The slurry can be directly prepared for coating, and meanwhile, in the subsequent rolling process, the inert shell is crushed, so that the effect of the metal lithium is fully exerted. The casing material does not affect the normal electrochemical process of the lithium battery at all. Meanwhile, as the powder, the use amount of lithium can be flexibly mastered, and the existing production process and formula system are not changed. Therefore, the inert core-shell structure metal lithium powder prepared by the invention is an ideal lithium battery cathode and a prelithiation material.
Description
Technical Field
The invention relates to an inert metal lithium powder with a core-shell structure, belonging to the technical field of lithium battery manufacturing.
Background
The current lithium battery technology does not use lithium metal as a negative electrode under the condition of not changing the existing positive and negative electrode system, and only simply changes a liquid electrolyte into a solid electrolyte, so that the energy density of the solid battery cannot be fundamentally improved. If the negative pole used metal lithium, not only promoted the energy density of whole electric core by a wide margin because can provide more lithium ion, can also effectively solve the lithium dendrite puncture diaphragm that exists in the liquid electrolyte, and the interface structure unstability scheduling problem that leads to takes place to last side reaction, the growth of lithium and precipitation with the liquid electrolyte under the high temperature.
At present, in order to supplement irreversible capacity loss (the quantity of lithium ions is reduced) of a lithium battery negative electrode in the first charging process, a battery factory hopes to supplement lithium by directly spraying metal lithium powder or lithium foil on a negative electrode pole piece through lithium supplementing equipment, so that the purposes of improving the first coulombic efficiency and the battery capacity are achieved. However, lithium metal as a raw material for lithium supplement is a highly reactive alkali metal, and is a very dangerous substance, and can catch fire and explode when it is not good. In the lithium supplement mode, the problem of lithium powder scattering is that the lithium powder has large specific surface area, is easy to float and has the risk of being inhaled by a human body; the problem of pressing the lithium belt is that the lithium belt cannot be pressed so thin, so that excessive lithium supplement can be caused, and potential safety hazards exist after long-term use. In addition to the danger of production and use process and high purchase cost of lithium supplement equipment, the requirement of production environment is quite severe because the metallic lithium can react with water violently.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides an inert metal lithium powder with a core-shell structure. The method is characterized in that active metal lithium is prepared into powder of 5-100 um, and one or more layers of inert brittle materials are coated on the surface of the prepared metal lithium powder, so that the prepared inert metal lithium powder does not react in air at the temperature of below 90 ℃, an NMP solvent or a reagent containing a small amount of water, and has good stability.
The invention adopts the following technical scheme:
an inert metal lithium powder with a core-shell structure is prepared by the following method:
(1) taking pure metal with the particle size of 5-100 mu mPutting lithium powder into a reactor filled with inert gas, introducing a certain amount of oxygen to react the surface of the pure metal lithium powder with the oxygen to generate a layer of lithium oxide shell, and preparing the lithium/Li-containing lithium powder2O inert lithium powder A with a core-shell structure;
(2) putting inert metal lithium powder A into a reactor filled with inert gas, then introducing a certain amount of carbon dioxide, heating the reactor to 100-160 ℃, reacting the carbon dioxide with lithium oxide to generate a lithium carbonate shell, and preparing the lithium/Li lithium carbonate shell2CO3Inert metal lithium powder B with a core-shell structure;
(3) adopting polyaniline as a polymer shell to carry out secondary coating on the inert metal lithium powder B prepared in the step (2) to obtain the product with Li/Li2CO3The inert lithium powder C with the PANI three-layer core-shell structure.
Preferably, in the step (1), the flow rate of oxygen gas is controlled to be 0.7L/h so that the produced Li2The thickness of the O shell is 100-500 nm.
Preferably, the content of lithium in the inert lithium powder A is 98-99%.
Preferably, the flow rate of carbon dioxide introduced in the step (2) is controlled to be 1L/h, so that Li finally generated2CO3The thickness of the shell is 100-200 nm.
Preferably, the content of lithium in the inert lithium powder B is 97-98%.
The specific method for coating polyaniline in the step (3) comprises the following steps: adding 10-100 g of polyaniline into 0.9-0.99 kg of solvent, heating to 50 ℃, and stirring for 1-2 hours to prepare a PANI solution with the concentration of 1-10% wt; adding 100g of inert lithium powder B into the prepared PANI solution, and fully dispersing the inert lithium powder B in the PANI solution by adopting a lossless laminar stirring mode to obtain an inert lithium powder B mixed solution; atomizing and drying the prepared inert lithium powder B mixed solution by adopting a spray drying mode, volatilizing a solvent for dissolving PANI, leaving the PANI on the surface of the inert lithium powder B, forming a PANI coating layer with the thickness of 50-500 nm on the surface of the inert lithium powder B, and finally preparing the lithium/Li mixed solution2CO3The inert lithium powder C with the PANI three-layer core-shell structure.
The solvent is N-methyl pyrrolidone, dimethylacetamide, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, carbon tetrachloride or trichloromethane.
All process links of the invention need to be carried out in an environment filled with inert gas and with controllable temperature.
The invention has the beneficial effects that: the inert lithium metal powder prepared by the invention does not react in air at the temperature of below 90 ℃, NMP solvent or other reagents containing a small amount of water. The slurry can be directly prepared for coating, and meanwhile, in the subsequent rolling process, the inert shell is crushed, so that the effect of the metal lithium is fully exerted. The casing material does not affect the normal electrochemical process of the lithium battery at all. Meanwhile, as the powder, the use amount of lithium can be flexibly mastered, and the existing production process and formula system are not changed. Therefore, the inert core-shell structure metal lithium powder prepared by the invention is an ideal lithium battery cathode and a prelithiation material.
Drawings
FIG. 1 the present invention has Li/Li2CO3A schematic principle diagram of a preparation process of the/PANI three-layer core-shell structure inert lithium powder C.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
An inert metal lithium powder with a core-shell structure is prepared by the following steps:
(1) taking 100g of pure lithium metal powder, putting the pure lithium metal powder into a reactor filled with inert gas, introducing 0.7L of oxygen in total at a flow rate of 0.7L/h, reacting the surface of the pure lithium metal powder with the oxygen to generate a layer of lithium oxide shell with the thickness of 100-500 nm, and preparing Li/Li2O-core-shell structure inert lithium powder A (the lithium content is 98-99%); the pure lithium metal powder used in the invention can be prepared into the pure lithium metal powder with the particle size of 5-100 mu m in metal atomization equipment which is fully sealed and filled with inert gas, such as equipment disclosed in patent 2017213506129 or other similar equipment;
(2) 500g of the prepared inert lithium powder A is put into a reaction filled with inert gasIntroducing 0.65L of carbon dioxide into the reactor at a flow rate of 1L/h, heating the reactor to 100-160 ℃ in the adding process, and reacting the carbon dioxide with the lithium oxide on the surface of the inert metal A to generate lithium carbonate to prepare Li/Li2CO3Inert metal lithium powder B (the lithium content is 97-98%) with the structure;
(3) adding 10-100 g of intrinsic polyaniline or doped polyaniline into 0.9-0.99 kg of solvent NMP, heating to 50 ℃, and stirring for 1-2 hours to prepare a PANI solution with the concentration of 1-10% wt; adding 100g of inert lithium powder B into the prepared PANI solution, and fully dispersing the inert lithium powder B in the PANI solution by adopting a lossless laminar stirring mode to obtain a mixture, wherein the content of the inert lithium powder B in the prepared mixture is 5-30 wt%; atomizing and drying the mixture of the inert lithium powder B and the PANI solution by adopting a spray drying mode, volatilizing a solvent for dissolving PNAI, remaining PANI on the surface of the inert lithium powder B, forming a PANI coating layer with the thickness of 50-500 nm on the surface of the inert lithium powder B, and finally preparing the Li/Li-containing composite material2CO3The inert lithium powder C with the PANI three-layer core-shell structure.
Example 2
An inert metal lithium powder with a core-shell structure is prepared by the following steps:
(1) taking 100g of pure lithium metal powder, putting the pure lithium metal powder into a reactor filled with inert gas, introducing 0.7L of oxygen in total at a flow rate of 0.7L/h, reacting the surface of the pure lithium metal powder with the oxygen to generate a layer of lithium oxide shell with the thickness of 100-500 nm, and preparing Li/Li2O-core-shell structure inert lithium powder A (the lithium content is 98-99%); the pure lithium metal powder used in the invention can be prepared into the pure lithium metal powder with the particle size of 5-100 mu m in metal atomization equipment which is fully sealed and filled with inert gas, such as equipment disclosed in patent 2017213506129 or other similar equipment;
(2) putting 500g of prepared inert lithium powder A into a reactor filled with inert gas, introducing 0.65L of carbon dioxide at the flow rate of 1L/h, heating the reactor to 100-160 ℃ in the adding process, and reacting the carbon dioxide with lithium oxide on the surface of the inert metal A to generate lithium carbonate to prepare Li/Li2CO3Inert metal lithium powder B of structure (lithium content)Amount 97-98%);
(3) adding 10-100 g of intrinsic polyaniline or doped polyaniline into 0.9-0.99 kg of solvent DMAC, heating to 50 ℃, stirring for 1-2 hours, and preparing a PANI solution with the concentration of 1-10% wt; adding 100g of inert lithium powder B into the prepared PANI solution, and fully dispersing the inert lithium powder B in the PANI solution by adopting a lossless laminar stirring mode to obtain a mixture, wherein the content of the inert lithium powder B in the prepared mixture is 5-30 wt%; atomizing and drying the mixture of the inert lithium powder B and the PANI solution by adopting a spray drying mode, volatilizing a solvent for dissolving PNAI, remaining PANI on the surface of the inert lithium powder B, forming a PANI coating layer with the thickness of 50-500 nm on the surface of the inert lithium powder B, and finally preparing the Li/Li-containing composite material2CO3The inert lithium powder C with the PANI three-layer core-shell structure.
Example 3
An inert metal lithium powder with a core-shell structure is prepared by the following steps:
(1) taking 100g of pure lithium metal powder, putting the pure lithium metal powder into a reactor filled with inert gas, introducing 0.7L of oxygen in total at a flow rate of 0.7L/h, reacting the surface of the pure lithium metal powder with the oxygen to generate a layer of lithium oxide shell with the thickness of 100-500 nm, and preparing Li/Li2O-core-shell structure inert lithium powder A (the lithium content is 98-99%); the pure lithium metal powder used in the invention can be prepared into the pure lithium metal powder with the particle size of 5-100 mu m in metal atomization equipment which is fully sealed and filled with inert gas, such as equipment disclosed in patent 2017213506129 or other similar equipment;
(2) putting 500g of prepared inert lithium powder A into a reactor filled with inert gas, introducing 0.65L of carbon dioxide at the flow rate of 1L/h, heating the reactor to 100-160 ℃ in the adding process, and reacting the carbon dioxide with lithium oxide on the surface of the inert metal A to generate lithium carbonate to prepare Li/Li2CO3Inert metal lithium powder B (the lithium content is 97-98%) with the structure;
(3) adding 10-100 g of intrinsic polyaniline or doped polyaniline into 0.9-0.99 kg of DMSO (dimethyl sulfoxide) solvent, heating to 50 ℃, and stirring for 1-2 hours to prepare a PANI solution with the concentration of 1-10% wt; 100g of inert lithium powder B was added to the preparedFully dispersing the inert lithium powder B in the PANI solution by adopting a lossless laminar stirring mode to prepare a mixture, wherein the content of the inert lithium powder B in the prepared mixture is 5-30 wt%; atomizing and drying the mixture of the inert lithium powder B and the PANI solution by adopting a spray drying mode, volatilizing a solvent for dissolving PNAI, remaining PANI on the surface of the inert lithium powder B, forming a PANI coating layer with the thickness of 50-500 nm on the surface of the inert lithium powder B, and finally preparing the Li/Li-containing composite material2CO3The inert lithium powder C with the PANI three-layer core-shell structure.
Example 4
An inert metal lithium powder with a core-shell structure is prepared by the following steps:
(1) taking 100g of pure lithium metal powder, putting the pure lithium metal powder into a reactor filled with inert gas, introducing 0.7L of oxygen in total at a flow rate of 0.7L/h, reacting the surface of the pure lithium metal powder with the oxygen to generate a layer of lithium oxide shell with the thickness of 100-500 nm, and preparing Li/Li2O-core-shell structure inert lithium powder A (the lithium content is 98-99%); the pure lithium metal powder used in the invention can be prepared into the pure lithium metal powder with the particle size of 5-100 mu m in metal atomization equipment which is fully sealed and filled with inert gas, such as equipment disclosed in patent 2017213506129 or other similar equipment;
(2) putting 500g of prepared inert lithium powder A into a reactor filled with inert gas, introducing 0.65L of carbon dioxide at the flow rate of 1L/h, heating the reactor to 100-160 ℃ in the adding process, and reacting the carbon dioxide with lithium oxide on the surface of the inert metal A to generate lithium carbonate to prepare Li/Li2CO3Inert metal lithium powder B (the lithium content is 97-98%) with the structure;
(3) adding 10-100 g of intrinsic polyaniline or doped polyaniline into 0.9-0.99 kg of DMF (dimethyl formamide) solvent, heating to 50 ℃, and stirring for 1-2 hours to prepare a PANI solution with the concentration of 1-10% wt; adding 100g of inert lithium powder B into the prepared PANI solution, and fully dispersing the inert lithium powder B in the PANI solution by adopting a lossless laminar stirring mode to obtain a mixture, wherein the content of the inert lithium powder B in the prepared mixture is 5-30 wt%; spray drying the mixture of inert lithium powder B and PANI solution, volatilizing solvent for dissolving PNAI, and mixing with water to obtain PNAI solutionThe PANI is retained on the surface of the inert lithium powder B, a PANI coating layer with the thickness of 50-500 nm is formed on the surface of the inert lithium powder B, and finally Li/Li is prepared2CO3The inert lithium powder C with the PANI three-layer core-shell structure.
Claims (7)
1. An inert metal lithium powder with a core-shell structure is characterized by being prepared by the following method:
(1) putting pure lithium metal powder with the particle size of 5-100 mu m into a reactor filled with inert gas, introducing a certain amount of oxygen, reacting the surface of the pure lithium metal powder with the oxygen to generate a layer of lithium oxide shell, and preparing the lithium/Li-doped lithium iron oxide shell2O inert lithium powder A with a core-shell structure;
(2) putting inert metal lithium powder A into a reactor filled with inert gas, then introducing a certain amount of carbon dioxide, heating the reactor to 100-160 ℃, reacting the carbon dioxide with lithium oxide to generate a lithium carbonate shell, and preparing the lithium/Li lithium carbonate shell2CO3Inert metal lithium powder B with a core-shell structure;
(3) adopting polyaniline as a polymer shell to carry out secondary coating on the inert metal lithium powder B prepared in the step (2) to obtain the product with Li/Li2CO3The inert lithium powder C with the PANI three-layer core-shell structure.
2. The lithium powder of an inert metal having a core-shell structure according to claim 1, wherein the flow rate of oxygen gas introduced in the step (1) is controlled to 0.7L/h so that Li is produced2The thickness of the O shell is 100-500 nm.
3. The inert lithium metal powder with a core-shell structure according to claim 1, wherein the content of lithium in the inert lithium powder A is 98-99%.
4. The inert lithium metal powder with a core-shell structure according to claim 1, wherein the flow rate of carbon dioxide introduced in step (2) is controlled to be 1L/h, so that Li finally generated is obtained2CO3Outer casingThe thickness is 100 to 200 nm.
5. The inert lithium metal powder with a core-shell structure according to claim 1, wherein the content of lithium in the inert lithium powder B is 97-98%.
6. The inert metal lithium powder with a core-shell structure according to claim 1, wherein the specific method for coating with polyaniline in step (3) is as follows: adding 10-100 g of polyaniline into 0.9-0.99 kg of solvent, heating to 50 ℃, and stirring for 1-2 hours to prepare a PANI solution with the concentration of 1-10% wt; adding 100g of inert lithium powder B into the prepared PANI solution, and fully dispersing the inert lithium powder B in the PANI solution by adopting a lossless laminar stirring mode to obtain an inert lithium powder B mixed solution; atomizing and drying the prepared inert lithium powder B mixed solution by adopting a spray drying mode, volatilizing a solvent for dissolving PANI, leaving the PANI on the surface of the inert lithium powder B, forming a PANI coating layer with the thickness of 50-500 nm on the surface of the inert lithium powder B, and finally preparing the lithium/Li mixed solution2CO3The inert lithium powder C with the PANI three-layer core-shell structure.
7. The lithium inert metal powder having a core-shell structure according to claim 6, wherein the solvent is N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, dimethylformamide, tetrahydrofuran, carbon tetrachloride or trichloromethane.
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| CN114094111A (en) * | 2020-07-31 | 2022-02-25 | 比亚迪股份有限公司 | Lithium supplement current collector, preparation method of lithium supplement current collector, negative electrode and lithium ion battery |
| CN114512674A (en) * | 2020-11-16 | 2022-05-17 | 比亚迪股份有限公司 | Negative pole piece and metal lithium battery |
| CN114864873A (en) * | 2022-04-20 | 2022-08-05 | 江苏正力新能电池技术有限公司 | Pre-lithiation method for negative plate, negative plate obtained by pre-lithiation method and secondary battery |
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