CN111864186B - Preparation method of three-dimensional porous metal lithium anode - Google Patents
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Abstract
The invention discloses a preparation method of a three-dimensional porous metal lithium anode, which comprises the following steps: dissolving a porous carbon material in a metal salt solution to obtain a mixed solution, stirring the mixed solution, and then sequentially washing, filtering and drying to obtain a black material; after the black material is subjected to heat treatment in an inert atmosphere, sequentially cleaning, filtering and drying to obtain a porous carbon material loaded with metal oxide nanoparticles; smearing a porous carbon material loaded with metal oxide nanoparticles as an active material to obtain a pole piece; and embedding lithium on the pole piece by a cold rolling or electro-deposition method to obtain the metal lithium anode. The preparation method of the nanocrystalline particle-loaded lithium metal active material provided by the invention is simple to operate and suitable for large-scale industrial production, and the obtained three-dimensional porous metal lithium anode not only can relieve huge volume expansion in the charging and discharging process, but also can solve the problem that a conductive framework is easy to block holes through lithium-philic nanoparticles.
Description
Technical Field
The invention relates to the field of energy storage materials and nanotechnology, in particular to a preparation method of a three-dimensional porous metal lithium anode.
Background
Lithium ion batteries have been rapidly developed in recent 30 years and are widely applied to mobile phones, digital cameras, electric vehicles and the like, but with the increase of the demand of people, the requirement on the energy density of the lithium ion batteries is higher and higher, the graphite anode is close to the theoretical limit, and in order to reach the energy density of 350Wh/kg or higher, the search for anode and cathode materials with higher energy density is a hotspot of researchers at present. The lithium metal anode is known as a holy cup in an anode material by virtue of ultrahigh specific energy, ultralow electrochemical potential and lower density, and lithium ternary batteries, lithium sulfur batteries, lithium oxygen batteries and the like assembled by the lithium metal anode have significant advantages of high energy density, low cost, environmental friendliness and the like, and become a research hotspot in the field of new energy batteries.
The reaction of the lithium metal anode in the charging and discharging process is Li+Different from the intercalation and deintercalation mechanism of a lithium ion battery, the host-free deposition of a lithium metal anode makes the volume effect of the lithium metal battery infinite in the charging and discharging processes, and the dendritic crystal growth problem in the lithium deposition process makes the coulombic efficiency of the metal lithium anode lower, which further deteriorates the battery performance of the metal lithium anode.
Disclosure of Invention
The invention aims to provide a preparation method of a three-dimensional porous metal lithium anode, and aims to solve the problem that the existing lithium metal anode has a high volume effect in the charging and discharging processes.
In order to achieve the above purpose, the preparation method of the three-dimensional porous metallic lithium anode provided by the invention comprises the following steps:
(1) dissolving a porous carbon material in a metal salt solution to obtain a mixed solution, stirring the mixed solution, and then sequentially washing, filtering and drying to obtain a black material;
(2) after the black material is subjected to heat treatment in an inert atmosphere, sequentially cleaning, filtering and drying to obtain a porous carbon material loaded with metal oxide nanoparticles;
(3) smearing a porous carbon material loaded with metal oxide nanoparticles as an active material to obtain a pole piece;
(4) and embedding lithium on the pole piece by a cold rolling or electro-deposition method to obtain the metal lithium anode.
Preferably, the pore diameter of the porous carbon material is 50-500nm, the wall thickness is 2-50nm, and the specific surface area is 50-500m3/g。
Preferably, the metal salt is one or more of copper nitrate, copper acetate, nickel nitrate, nickel acetate, bismuth nitrate, bismuth acetate, magnesium nitrate, magnesium acetate, zinc nitrate, zinc acetate, indium nitrate, indium acetate, tin nitrate, tin acetate, silver nitrate, and silver acetate.
Preferably, the solvent of the metal salt solution is water and ethanol.
Preferably, the mixing temperature in the step (1) is 5-80 ℃, the mixing molar ratio is 1-100, and the mixing time is 10-600 min.
Preferably, the step (1) further comprises: dissolving the black material in the same metal salt solution with higher concentration, mixing and stirring, and then sequentially washing, filtering and drying, repeating the steps for a plurality of times to obtain the final black material.
Preferably, the gas of the inert atmosphere in the step (2) is one of argon, helium and neon, and the gas flow rate is 10-1000 sccm.
Preferably, the heat treatment temperature in the step (2) is 100-.
Preferably, the thickness of the lithium metal strip used in the cold rolling in the step (4) is 10-100 μm, and the cold rolling temperature is 10-100 ℃.
Preferably, the current density used for electrodeposition in the step (4) is 0.1-10mAh/cm2The deposition time is 10-600 min.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the nanocrystalline particle-loaded lithium metal active material is simple to operate and suitable for large-scale industrial production, the obtained three-dimensional porous metal lithium anode can relieve huge volume expansion in the charging and discharging process, the problem that a conductive framework is easy to block holes can be solved through lithium-philic nano particles, the advantages of conductivity and lithium-philic property are taken into consideration, and the preparation of the high-specific-energy long-cycle metal lithium anode can be realized.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited thereto.
Example 1
Preparing materials: taking 0.24g of porous carbon material (aperture 80nm, wall thickness 5nm, specific surface area 285 cm)3Pore volume 78%) 1 is added00mL of 0.1M copper nitrate water/ethanol (volume ratio 1: 1) solution, stirring for 3 hours at 30 ℃, cleaning, filtering and drying, then adding the material into 1M copper nitrate solution, stirring for 1 hour, cleaning, filtering and drying to obtain a black material. And (3) placing the black material in a tubular furnace, adopting argon atmosphere, wherein the gas flow is 20sccm, the heating rate is 5 ℃/min, the heat treatment temperature is 200 ℃, the heat preservation time is 2h, and the cooling rate is 5 ℃/min, cleaning, filtering and drying the obtained composite porous carbon material, and obtaining a solid material, namely the porous carbon material loaded with the metal oxide nano particles.
Electrochemical performance: and (3) taking a porous carbon material loaded by metal oxide nanoparticles as an active material smear, wherein the thickness of a pole piece is 60 microns, and cold-rolling the active material smear and a lithium belt with the thickness of 20 microns at 50 ℃ to obtain the composite lithium anode. Matched lithium iron phosphate (5 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 1C with the performance parameters shown in table 1.
Comparative example 1
The difference from example 1 is that the composite material obtained is not sufficiently homogeneous when mixed directly in a high-concentration solution without gradient mixing.
Preparing materials: 0.24g of porous carbon material (same as in example 1) was added to a 1M copper nitrate water/ethanol (volume ratio 1: 1) solution, stirred for 1 hour, washed, filtered and dried to obtain a black material. And (3) placing the black material in a tubular furnace, adopting argon atmosphere, wherein the gas flow is 20sccm, the heating rate is 5 ℃/min, the heat treatment temperature is 200 ℃, the heat preservation time is 2h, and the cooling rate is 5 ℃/min, cleaning, filtering and drying the obtained composite porous carbon material, and obtaining a solid material, namely the porous carbon material loaded with the metal oxide nano particles.
Electrochemical performance: and (3) taking a porous carbon material loaded by metal oxide nanoparticles as an active material smear, wherein the thickness of a pole piece is 60 microns, and cold-rolling the active material smear and a lithium belt with the thickness of 20 microns at 50 ℃ to obtain the composite lithium anode. Matched lithium iron phosphate (5 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 1C with the performance parameters shown in table 1.
Comparative example 2
The difference from example 1 is that no metal oxide nanoparticle loading was performed.
A porous carbon material (same as example 1) is used as an active material smear, the thickness of a pole piece is 60 mu m, and the active material smear is cold-rolled with a lithium belt with the thickness of 20 mu m at the temperature of 50 ℃ to obtain the composite lithium anode. Matched lithium iron phosphate (5 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 1C with the performance parameters shown in table 1.
TABLE 1
| Sample (I) | Specific capacity of first ring | 100 cycles average coulombic efficiency | Number of turns with coulombic efficiency lower than 80% |
| Example 1 | 141.9mAh/g | 99.95％ | 542 |
| Comparative example 1 | 138.4mAh/g | 99.6％ | 347 |
| Comparative example 2 | 120.5mAh/g | 90.4％ | 98 |
Example 2
Preparing materials: taking 0.24g of porous carbon material (aperture 150nm, wall thickness 7nm, specific surface area 625 cm)3Per g, pore volume 95%), 100mL of 0.01M nickel nitrate aqueous solution, stirring at 50 ℃ for 4 hours, washing, filtering and drying, adding the material into 0.1M nickel nitrate aqueous solution, stirring for 2 hours, washing, filtering and drying, adding the material into 1M nickel nitrate aqueous solution, stirring for 1 hour, washing, filtering and drying to obtain black material. And (3) placing the black material in a tubular furnace, adopting argon atmosphere, wherein the gas flow is 40sccm, the heating rate is 10 ℃/min, the heat treatment temperature is 300 ℃, the heat preservation time is 4h, and the cooling rate is 3 ℃/min, cleaning, filtering and drying the obtained composite porous carbon material, and obtaining a solid material, namely the porous carbon material loaded with the metal oxide nano particles.
Electrochemical performance: the smear is made of porous carbon material loaded by metal oxide nanoparticles as active material, the thickness of the pole piece is 100 μm and is 1mA/cm2And (4) depositing for 12 hours at the current density of (2) to obtain the composite lithium anode. Matched lithium iron phosphate (2 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 5C with the performance parameters shown in table 1.
Example 3
Preparing materials: taking 0.24g of porous carbon material (aperture 200nm, wall thickness 10nm, specific surface area 518 cm)3Pore volume 90%), copper acetate water/ethanol was added at a concentration of 0.05M (volume ratio 1: 1) to the solution, stirred at 25 ℃ for 3 hours, washed, filtered and dried, and then the material was added to 0.5M copper acetate water/ethanol (volume ratio 2: 1) stirring the solution at room temperature for 2 hours, cleaning, filtering and drying, then adding the material into a copper acetate aqueous solution with the concentration of 2M, stirring the solution at room temperature for 1 hour, cleaning, filtering and drying to obtain a black material. Placing the black material in a tubular furnace in argon atmosphere, wherein the gas flow is 80sccm, the heating rate is 1 ℃/min, the heat treatment temperature is 200 ℃, the heat preservation time is 4h, and the cooling rate is 1 ℃/min, so that the obtained composite porous carbon material is obtainedAnd cleaning, filtering and drying to obtain the solid material, namely the porous carbon material loaded with the metal oxide nano particles.
Electrochemical performance: and (3) taking a porous carbon material loaded by metal oxide nanoparticles as an active material smear, wherein the thickness of a pole piece is 50 microns, and cold-rolling the active material smear and a lithium belt with the thickness of 10 microns at the temperature of 20 ℃ to obtain the composite lithium anode. Matched sulfur carbon anode (3 mg/cm)2S) assembling the positive electrode into a full cell, and testing the performance of the cell at 0.5C, wherein the performance parameters are shown in Table 2.
Example 4
Preparing materials: taking 0.24g of porous carbon material (aperture 300nm, wall thickness 20nm, specific surface area 165 cm)3Pore volume 85%), bismuth nitrate water/ethanol at a concentration of 0.06M (volume ratio 1: 3) stirring for 4 hours at room temperature, cleaning, filtering and drying; adding the materials into 0.8M bismuth nitrate water/ethanol (volume ratio is 1: 1) solution, stirring for 1 hour, cleaning, filtering and drying; adding the materials into a 1.5M bismuth nitrate water/ethanol (volume ratio is 2: 1) solution, stirring for 1 hour, cleaning, filtering and drying; a black material was obtained. And (3) placing the black material in a tubular furnace, adopting argon atmosphere, wherein the gas flow is 100sccm, the heating rate is 5 ℃/min, the heat treatment temperature is 250 ℃, the heat preservation time is 6h, and the cooling rate is 5 ℃/min, cleaning, filtering and drying the obtained composite porous carbon material, and obtaining a solid material, namely the metal oxide nano particle loaded porous carbon material.
Electrochemical performance: the smear is made of porous carbon material loaded by metal oxide nanoparticles, the thickness of the pole piece is 200 μm, and the thickness is 10mA/cm2And (4) depositing for 4 hours at the current density of (2) to obtain the composite lithium anode. Matched sulfur carbon anode (6 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 2C with the performance parameters shown in table 1.
Example 5
Preparing materials: taking 0.24g of porous carbon material (aperture 400nm, wall thickness 50nm, specific surface area 96 cm)3Per g, pore volume 75%), added to 0.04M ethanol solution of bismuth acetate, stirred at 30 deg.C for 4 hours, washed, filtered, dried, and then added to the solutionStirring for 4 hours in 1M ethanol solution of bismuth acetate, cleaning, filtering and drying to obtain a black material. And (3) placing the black material in a tubular furnace, adopting argon atmosphere, wherein the gas flow is 200sccm, the heating rate is 7 ℃/min, the heat treatment temperature is 350 ℃, the heat preservation time is 5h, and the cooling rate is 8 ℃/min, cleaning, filtering and drying the obtained composite porous carbon material, and obtaining a solid material, namely the porous carbon material loaded with the metal oxide nano particles.
Electrochemical performance: and (3) taking a porous carbon material loaded by metal oxide nanoparticles as an active material smear, wherein the thickness of a pole piece is 300 mu m, and cold-rolling the active material smear and a lithium belt with the thickness of 80 mu m at 80 ℃ to obtain the composite lithium anode. Matching NCM (622) (5 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 0.5C with the performance parameters shown in table 2.
TABLE 2
| Sample (I) | Specific capacity of first ring | 100 cycles average coulombic efficiency | Number of turns with coulombic efficiency lower than 80% |
| Example 2 | 140.5mAh/g | 99.1％ | 196 |
| Example 3 | 1158mAh/g | 98.8％ | 210 |
| Example 4 | 1208mAh/g | 98.4％ | 173 |
| Example 5 | 196.4mAh/g | 99.2％ | 385 |
Example 6
Preparing materials: taking 0.24g of porous carbon material (aperture 500nm, wall thickness 60nm, specific surface area 335 cm)3Pore volume 65%), magnesium nitrate water/ethanol was added at a concentration of 0.08M (volume ratio 1: 6) to the solution, the mixture was stirred at 30 ℃ for 3 hours, washed, filtered and dried, and then the resultant was added to magnesium nitrate water/ethanol (volume ratio 3: 1) stirring the solution for 2 hours, cleaning, filtering and drying to obtain a black material. And (3) placing the black material in a tubular furnace, adopting argon atmosphere, wherein the gas flow is 300sccm, the heating rate is 6 ℃/min, the heat treatment temperature is 400 ℃, the heat preservation time is 3h, and the cooling rate is 4 ℃/min, cleaning, filtering and drying the obtained composite porous carbon material, and obtaining a solid material, namely the porous carbon material loaded with the metal oxide nano particles.
Electrochemical performance: the smear is made of porous carbon material loaded by metal oxide nanoparticles, the thickness of the pole piece is 350 μm, and the thickness is 4mA/cm2And (4) depositing for 12 hours at the current density of (2) to obtain the composite lithium anode. Matched lithium iron phosphate (8 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 1C with the performance parameters shown in table 3.
Example 7
Preparing materials: taking 0.24g of porous carbon material (aperture 600nm, wall thickness 40nm, specific surface area 318 cm)3Per g, pore volume 75%), magnesium acetate water/ethanol (volume ratio 1) was added at a concentration of 0.1M: 4) to the solution, stirred at 40 ℃ for 3 hours, washed, filtered and dried, and then the resultant was added to 1M magnesium acetate water/ethanol (volume ratio 2: 1) stirring the solution for 1 hour at room temperature, washing, filtering and drying to obtain a black material. And (3) placing the black material in a tubular furnace, adopting argon atmosphere, wherein the gas flow is 500sccm, the heating rate is 15 ℃/min, the heat treatment temperature is 450 ℃, the heat preservation time is 2h, and the cooling rate is 10 ℃/min, cleaning, filtering and drying the obtained composite porous carbon material, and obtaining a solid material, namely the metal oxide nano particle loaded porous carbon material.
Electrochemical performance: and (3) taking a porous carbon material loaded by metal oxide nanoparticles as an active material smear, wherein the thickness of a pole piece is 250 micrometers, and cold-rolling the active material smear and a lithium belt with the thickness of 50 micrometers at 70 ℃ to obtain the composite lithium anode. Matched lithium iron phosphate (3 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 2C with performance parameters as shown in table 3.
Example 8
Preparing materials: taking 0.24g of porous carbon material (the aperture is 700nm, the wall thickness is 35nm, and the specific surface area is 497 cm)3Pore volume 88%), zinc nitrate water/ethanol was added at a concentration of 0.08M (volume ratio 3: 1) to the solution, stirred at 50 ℃ for 4 hours, washed, filtered and dried, and then the material was added to a 1M zinc nitrate water/ethanol (volume ratio 3: 1) stirring the solution for 1 hour, cleaning, filtering and drying to obtain a black material. And (3) placing the black material in a tubular furnace, adopting argon atmosphere, wherein the gas flow is 400sccm, the heating rate is 10 ℃/min, the heat treatment temperature is 500 ℃, the heat preservation time is 1h, and the cooling rate is 8 ℃/min, cleaning, filtering and drying the obtained composite porous carbon material, and obtaining a solid material, namely the porous carbon material loaded with the metal oxide nano particles.
Electrochemical performance: the smear is made of porous carbon material loaded by metal oxide nanoparticles as active material, the thickness of the pole piece is 150 μm, and the thickness is 5mA/cm2And (4) depositing for 4 hours at the current density of (2) to obtain the composite lithium anode. Matched lithium iron phosphate (10 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 0.2C with the performance parameters shown in table 3.
Example 9
Preparing materials: 0.24g of porous carbon material (aperture 800nm, wall thickness 100nm, specific surface area 187 cm)3Pore volume 72%), indium acetate water/ethanol was added at a concentration of 0.02M (volume ratio 1: 2) the solution was stirred at 60 ℃ for 8 hours, washed, filtered and dried, and then the material was added to 1M indium acetate water/ethanol (volume ratio 2: 1) stirring the solution for 1 hour, cleaning, filtering and drying to obtain a black material. Placing the black material in a tubular furnace, adopting argon atmosphere, wherein the gas flow is 600sccm, the heating rate is 0.5 ℃/min, the heat treatment temperature is 200 ℃, the heat preservation time is 10h, and the cooling rate is 2 ℃/min, cleaning, filtering and drying the obtained composite porous carbon material, and obtaining a solid material, namely the porous carbon material loaded with the metal oxide nano particles.
Electrochemical performance: and (3) taking a porous carbon material loaded by metal oxide nanoparticles as an active material smear, wherein the thickness of a pole piece is 120 mu m, and cold-rolling the active material smear and a lithium belt with the thickness of 40 mu m at the temperature of 60 ℃ to obtain the composite lithium anode. Matched sulfur carbon anode (6 mg/cm)2S) assembling the positive electrode into a full cell, and testing the performance of the cell at 0.2C, wherein the performance parameters are shown in Table 3.
Example 10
Preparing materials: taking 0.24g of porous carbon material (aperture 900nm, wall thickness 80nm, specific surface area 65 cm)3Pore volume 64%), silver nitrate water/ethanol was added at a concentration of 0.05M (volume ratio 1: 10) to the solution, stirred at 25 ℃ for 5 hours, washed, filtered and dried, and then added to a 0.6M silver nitrate water/ethanol (volume ratio 1: 6) to the solution, stirred at 25 ℃ for 3 hours, washed, filtered and dried, and then the material was added to a 1.2M silver nitrate water/ethanol (volume ratio 1: 2) stirring the solution at 25 deg.C for 2 hr, cleaning, filtering, drying, adding the material into 2.5M silver nitrate aqueous solution, stirring at 25 deg.C for 1 hr, cleaning, filtering, and drying to obtain black material. Placing the black material in a tube furnace under argon atmosphere, wherein the gas flow is 700sccm, the heating rate is 1 ℃/min, the heat treatment temperature is 300 ℃, the heat preservation time is 4h, and the cooling rate is 2 ℃/min to obtain the black materialThe composite porous carbon material is cleaned, filtered and dried, and the obtained solid material is the porous carbon material loaded by the metal oxide nano particles.
Electrochemical performance: the smear is made of active material of porous carbon material loaded with metal oxide nanoparticles, and the thickness of the pole piece is 160 μm at 2mA/cm2And (3) depositing for 10 hours at the current density of (2) to obtain the composite lithium anode. Match NCM (811) (3.6 mg/cm)2) The positive electrode was assembled into a full cell and the cell performance was tested at 0.5C with the performance parameters shown in table 3.
TABLE 3
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (9)
1. A method of making a three-dimensional porous metallic lithium anode, comprising the steps of:
(1) dissolving a porous carbon material in a metal salt solution to obtain a mixed solution, stirring the mixed solution, and then sequentially washing, filtering and drying to obtain a black material; dissolving the black material in the same metal salt solution with higher concentration, mixing and stirring, and then sequentially washing, filtering and drying, repeating the steps for a plurality of times to obtain the final black material;
(2) after the black material is subjected to heat treatment in an inert atmosphere, sequentially cleaning, filtering and drying to obtain a porous carbon material loaded with metal oxide nanoparticles;
(3) smearing a porous carbon material loaded with metal oxide nanoparticles as an active material to obtain a pole piece;
(4) and embedding lithium on the pole piece by a cold rolling or electro-deposition method to obtain the metal lithium anode.
2. The method of preparing a three-dimensional porous metallic lithium anode of claim 1,
the porous carbon material has a pore diameter of 50-500nm, a wall thickness of 2-50nm, and a specific surface area of 50-500m2/g。
3. The method for preparing a three-dimensional porous metallic lithium anode according to claim 1, wherein the metal salt is one or more of copper nitrate, copper acetate, nickel nitrate, nickel acetate, bismuth nitrate, bismuth acetate, magnesium nitrate, magnesium acetate, zinc nitrate, zinc acetate, indium nitrate, indium acetate, tin nitrate, tin acetate, silver nitrate, and silver acetate.
4. The method of preparing a three-dimensional porous metallic lithium anode of claim 1, wherein the solvent of the metal salt solution is water and ethanol.
5. The method of preparing a three-dimensional porous metallic lithium anode according to claim 1, wherein the mixing temperature in the step (1) is 5 to 80 ℃, the mixing molar ratio is 1 to 100, and the mixing time is 10 to 600 min.
6. The method for preparing a three-dimensional porous metallic lithium anode according to any one of claims 1 to 5, wherein the inert atmosphere gas in the step (2) is one of argon, helium and neon, and the gas flow rate is 10 to 1000 sccm.
7. The method for preparing the three-dimensional porous metal lithium anode as claimed in claim 6, wherein the heat treatment temperature in the step (2) is 100-.
8. The method for preparing a three-dimensional porous metallic lithium anode according to any one of claims 1 to 5, wherein the thickness of the metallic lithium strip used in the cold rolling in the step (4) is 10 to 100 μm, and the cold rolling temperature is 10 to 100 ℃.
9. The method for preparing a three-dimensional porous metallic lithium anode according to any one of claims 1 to 5, wherein the electrodeposition in the step (4) is carried out using a current density of 0.1 to 10mA/cm2The deposition time is 10-600 min.
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