CN112259910A - Cubic hole carbon coating diaphragm of lithium metal battery and preparation method thereof - Google Patents
Cubic hole carbon coating diaphragm of lithium metal battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cubic hole carbon coating diaphragm of a lithium metal battery and a preparation method thereof, belonging to the technical field of battery materials. The coating material of the lithium metal battery coating diaphragm provided by the invention has a nano-flake structure and is provided with a cubic hole, and the cubic hole is surrounded by carbon walls; the cubic holes are uniform in size, the side length is 20-28 nm, and the cubic holes are closely stacked and arranged. The coating material is obtained by removing the template after carbonizing carbon-containing organic matters. The coating material electrolyte has good wettability, and the utilization efficiency of the electrolyte is improved; the interface impedance can be reduced, and the multiplying power capability of the lithium metal battery is improved.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a cubic hole carbon coating diaphragm of a lithium metal battery and a preparation method thereof.
Background
The rapid development of mobile electronic devices and electric automobiles has made urgent need for energy storage and power supply of lithium secondary batteries with higher energy density. However, lithium ion batteries are still widely used in the market at present, and the negative electrode adopts intercalation compounds such as graphite and the like to store lithium ions, so that the theoretical capacity is difficult to meet the application requirement. The lithium metal negative electrode has the highest theoretical specific capacity (3860mAh/g) and the lowest electrochemical potential (-3.04V vs. standard hydrogen electrode), and is an ideal choice of the negative electrode material. However, lithium metal has ultrahigh reaction activity, and infinite volume expansion can be caused by uneven deposition in the charge-discharge reaction process, so that a surface SEI film is cracked to generate lithium dendrites, dead lithium is generated in subsequent circulation, and the utilization rate of the lithium metal is reduced; the constantly broken SEI film causes the lithium metal to continuously react with the electrolyte, so that the electrolyte is consumed, the irreversible loss of the active material of the negative electrode is caused, and the interface resistance is improved by the generated thick SEI film.
The current research shows that the dendrite and pulverization problems of the lithium metal negative electrode are one of the important reasons for influencing the practicability of the lithium metal battery. Common modification strategies are the construction of in-situ SEI films and artificial SEI films. The in-situ SEI film modification is to generate an enhanced SEI film on the surface of the negative electrode in situ by regulating and controlling electrolyte components such as electrolyte additives, co-solvents and lithium salt types and concentrations, stabilize the interface between the negative electrode and an electrolyte and guide the uniform deposition of lithium ions. However, the SEI film obtained by the method has the defects of difficult control of the components and the morphology, and the effective components are continuously consumed in the battery cycle process and finally lose the protection effect. The components and the effects of the artificial SEI film are similar to those of the SEI film generated in situ, the artificial SEI film can be generated in advance through the chemical reaction of lithium metal before the battery is assembled, and can also be directly coated on the surface of the lithium metal after being prepared, but the artificial SEI film is often thicker, the interface impedance can be increased, and the engineering amplification is difficult.
The lithium metal cathode is protected through diaphragm modification, the method is simpler, and compared with the harsh reaction environment of lithium metal, the method is easier to operate and safer. However, the application of the separator modification in the lithium metal negative electrode protection is yet to be studied and reported.
Disclosure of Invention
The invention provides a lithium metal battery cubic hole carbon coating diaphragm and a preparation method thereof, wherein the coating material of the coating diaphragm is provided with cubic holes, and the deposition behavior of lithium metal is regulated through the structure; the coating material has good electrolyte wettability, and the utilization efficiency of the electrolyte is improved; the interface impedance can be reduced, and the multiplying power capability of the lithium metal battery is improved.
The invention firstly provides a coating material of a lithium metal battery coating diaphragm, which has a nano-flake structure and is provided with cubic holes, and the cubic holes are surrounded by carbon walls; the cubic holes are uniform in size, the side length is 20-28 nm, and the cubic holes are closely stacked and arranged.
The coating material is obtained by removing the template after carbonizing the carbon-containing organic matter;
the coating material is characterized in that the density of the cubic holes is controlled by controlling the molar ratio of the template to the carbon-containing organic matter, and the thickness and the size of the nano-sheet are controlled by controlling the molar ratio of the carbon-containing organic matter to the sodium sulfate.
Specifically, the carbon-containing organic matter is at least one of sodium gluconate, sodium acetate and sodium oleate.
The invention also provides a preparation method of the coating material, which comprises the following steps:
(1) mixing an inorganic salt template with the carbon-containing organic matter to obtain a mixture of the template and a precursor;
(2) adding sodium sulfate into the mixture obtained in the step (1) to obtain a pre-carbonized material;
(3) heating the pre-carbonized material in an inert atmosphere to obtain a cubic pore carbon material with an inorganic salt template inside;
(4) removing the inorganic salt template from the cubic pore carbon material with the inorganic salt template inside to obtain a pure cubic pore carbon material;
(5) and (4) heating the pure cubic pore carbon material prepared in the step (4) in an inert atmosphere to obtain cubic pore carbon, namely the coating material.
In the preparation method, in the step (1), the inorganic salt template is at least two of ferric chloride, manganese chloride and zinc chloride.
The molar ratio of the reaction product of the inorganic salt template to the carbon-containing organic matter is 1: 4-20.
The step (1) further comprises the steps of heating and cooling to room temperature after mixing; specifically, the heating temperature is 70-120 ℃; the temperature can be 70-100 ℃; the heat preservation time is 3-5 h; specifically, the time can be 3 hours.
In the mixing step, the inorganic salt template is firstly dissolved in a small amount of water, and then the carbon-containing organic matter is added.
Specifically, the inorganic salt template is any one of the following:
1) ferric chloride and manganese chloride; specifically, the molar ratio of the ferric chloride to the manganese chloride is 2-5: 1; specifically 2: 1;
2) ferric chloride and zinc chloride; specifically, the molar ratio of the ferric chloride to the zinc chloride is 2-5: 1; specifically 2: 1;
3) ferric chloride, manganese chloride and zinc chloride; specifically, the molar ratio of ferric chloride to (the sum of manganese chloride and zinc chloride) is 2-5: 1.
In the preparation method, in the step (2), the molar ratio of the carbon-containing organic substance to the sodium sulfate is 1: 4-20.
In the step (2), the sodium sulfate is in a powder form.
In the above preparation method, in the step (3) and the step (5), the inert atmosphere is at least one of a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.
In the step (3), the heating temperature is 400-700 ℃, and specifically 500-700 ℃; the heat preservation time is 1-5 h, and specifically can be 3-4 h; the heating rate is 1-5 ℃/min; specifically, it can be 5 ℃/min.
In the step (5), the heating temperature is 800-1100 ℃, and specifically 800-1000 ℃; the heat preservation time is 1-5 h, and specifically can be 3-4 h; the heating rate is 3-10 ℃/min, and can be 3 ℃/min or 5 ℃/min.
In the preparation method, in the step (4), the cubic pore carbon material with the inorganic salt template inside is soaked in an acid solution to remove the inorganic salt template.
Specifically, the acid solution is a dilute hydrochloric acid solution;
the soaking time is 6-10 h; specifically, the time can be 6 h; the temperature of the soaking is room temperature.
The room temperature is a temperature known to a person skilled in the art, namely 15-40 ℃; specifically, the temperature can be 15-30 ℃.
In the step (4), the method further comprises the steps of cleaning and drying after removing the inorganic salt template.
The invention also provides a lithium metal battery coating diaphragm which comprises the coating material and a base film.
In the lithium metal battery coating diaphragm, the base film is a PP film.
The preparation method of the lithium metal battery coating diaphragm comprises the following steps: and mixing the coating material with a binder, and coating the mixture on the base film to obtain the lithium metal battery coating diaphragm.
In the preparation method, the mass ratio of the coating material to the binder is 4-9: 1; specifically, the ratio can be 9: 1.
The binder is at least one of polyvinylidene fluoride resin (PVDF), polyvinylpyrrolidone (PVP) and polyethylene oxide (PEO).
In the above preparation method, the coating material and the binder are mixed by grinding.
Finally, the invention also provides a lithium battery comprising the lithium metal battery coating diaphragm.
The invention has the following beneficial effects:
1) the coating material of the cubic hole carbon coating diaphragm of the lithium metal battery has a nano-flake structure and is provided with cubic holes, and the deposition behavior of lithium metal is regulated through the structure;
2) the coating material of the cubic pore carbon coating diaphragm of the lithium metal battery has a hollow structure and a three-dimensional porous structure, and the material has a large specific surface area, so that the local current density can be effectively reduced, the electric field distribution is uniform, the growth of dendritic crystals is inhibited, and the lithium deposition is more compact and uniform;
3) the coating material of the cubic hole carbon coating diaphragm of the lithium metal battery can generate lithiation reaction in the charging and discharging processes, so that the interface is more lithium-philic, and the activation energy of lithium adsorption can be reduced;
4) the coating material of the cubic hole carbon coating diaphragm of the lithium metal battery has good electrolyte wettability and strong electrolyte adsorption capacity, effectively reduces the concentration gradient of lithium ions, and improves the utilization efficiency of the electrolyte;
5) the coating material of the cubic hole carbon coating diaphragm of the lithium metal battery can effectively reduce the interface impedance and the nucleation overpotential of lithium deposition, thereby improving the lithium ion transfer capacity and the multiplying power capacity of the lithium metal battery;
6) the preparation method of the cubic hole carbon coating diaphragm of the lithium metal battery is simple to operate, green and environment-friendly and is easy for large-scale production.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) image of cubic pore carbon prepared in step (5) of example 1.
Fig. 2 is a graph of electrolyte wettability of the cubic-pore carbon-coated separator prepared in example 1 and a blank separator.
Fig. 3 is a graph comparing the coulombic efficiency of a cubic pore carbon coated separator assembled lithium copper battery prepared in example 1 with that of a blank separator assembled lithium copper battery under high rate conditions.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
The experimental procedures in the following examples are conventional unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
PVDF (polyvinylidene fluoride resin) binder, as in the examples below, was obtained from Shanghai Allantin Biotech Co., Ltd;
the thickness of the PP separator was 30 μm and was purchased from Celgard.
Assembly and testing of lithium copper batteries made in the following examples: the copper foil is used as a positive electrode, the metal lithium sheet is used as a negative electrode, and the electrolyte consists of lithium bis (trifluoromethylsulfonyl) imide and a mixed solvent of ethylene glycol dimethyl ether and 1, 3-dioxolane in a volume ratio of 1:1, wherein the concentration of the lithium bis (trifluoromethylsulfonyl) imide is 1 mol/L; the diaphragm adopts a coating diaphragm or a blank diaphragm (PP diaphragm) prepared in the embodiment, and a CR2016 type lithium metal battery is formed in a glove box; and (3) carrying out electrochemical performance test on the assembled lithium metal battery by adopting a blue test system, wherein the test temperature is 30 ℃.
Example 1
(1) 1.1536g of ferric chloride and 0.4474g of manganese chloride are dissolved in a small amount (5mL) of deionized water, 20g of sodium oleate is added and mixed uniformly, the mixture is heated to 80 ℃ and then is kept warm for 3h and cooled to room temperature, and a mixture of a template and a precursor is obtained;
(2) adding 40g of powdered sodium sulfate into the mixture obtained in the step (1), and fully and uniformly mixing to obtain a pre-carbonized material;
(3) heating the pre-carbonized material to 700 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 4h, and cooling to obtain a cubic pore carbon material with an inorganic salt template inside;
(4) placing the cubic pore carbon material with the inorganic salt template in dilute hydrochloric acid for 6 hours to remove the template, and cleaning and drying (drying at 100 ℃ for 24 hours) to obtain a pure cubic pore carbon material;
(5) heating the cubic pore carbon material to 800 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 4h, and cooling to obtain cubic pore carbon;
(6) and (3) grinding and uniformly mixing 0.6g of the cubic pore carbon obtained in the step (5) with 0.067g of PVDF binder, and coating the mixture on a PP diaphragm to obtain the cubic pore carbon coating diaphragm.
As can be seen from the TEM image in fig. 1, the coated separator coated carbon material prepared in this example had a nano-flake structure with cubic pores, the structure being obtained by carbonizing an organic substance and removing a template; the cubic holes are uniform in size, the side length is 20nm, and the cubic holes are closely stacked and arranged.
As can be seen from the electrolyte wettability chart in FIG. 2, the contact angle of the cubic pore carbon coating membrane to the electrolyte is 6.7 degrees, which is smaller than that of the blank membrane (43.1 degrees), and the electrolyte of the cubic pore carbon coating membrane is completely soaked after 3 s; in contrast, the blank separator still had an electrolyte contact angle of 35.3 ° after 15 s.
Two lithium copper batteries were assembled, differing only in that: one with a cubic pore carbon coated membrane and one with a blank membrane. The lithium deposition and extraction capacities of the two lithium copper batteries are both 2mAh/cm2The current density is 6mA/cm2. As can be seen from the test results of fig. 3, the coulombic efficiency remained 95.59% after 75 cycles of stabilization for the lithium copper battery using the cubic pore carbon coated separator, compared to 82.76% after 75 cycles for the lithium copper battery using the blank separator.
Example 2
(1) 1.1536g of ferric chloride and 0.4474g of manganese chloride are dissolved in a small amount (5mL) of deionized water, 10g of sodium oleate is added, the mixture is fully and uniformly mixed, the mixture is heated to 80 ℃, and then the mixture is cooled to room temperature after being kept warm for 3h, so that a mixture of a template and a precursor is obtained;
(2) adding 40g of powdered sodium sulfate into the mixture obtained in the step (1), and fully and uniformly mixing to obtain a pre-carbonized material;
(3) heating the pre-carbonized material to 500 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 4h, and cooling to obtain a cubic pore carbon material with an inorganic salt template inside;
(4) placing the cubic pore carbon material with the inorganic salt template in dilute hydrochloric acid for 6 hours to remove the template, and cleaning and drying (drying at 100 ℃ for 24 hours) to obtain a pure cubic pore carbon material;
(5) heating the cubic pore carbon material to 800 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 4h, and cooling to obtain cubic pore carbon;
(6) and (3) grinding and uniformly mixing 0.6g of the cubic pore carbon obtained in the step (5) with 0.067g of PVDF binder, and coating the mixture on a PP diaphragm to obtain the cubic pore carbon coating diaphragm.
The test results are similar to those of fig. 1, and the coated separator coated carbon material prepared in this example has a nano-flake structure with cubic pores, the structure being obtained by carbonizing an organic substance and removing a template; the cubic holes are uniform in size, the side length is 27nm, and the cubic holes are closely stacked and arranged.
The test result is similar to that of FIG. 2, the contact angle of the cubic pore carbon coating diaphragm to the electrolyte is 7.2 degrees, which is smaller than that of the blank diaphragm (43.2 degrees), and the electrolyte of the cubic pore carbon coating diaphragm is completely soaked after 3 s; in contrast, the blank separator still had an electrolyte contact angle of 35.5 ° after 15 s.
Two lithium copper batteries were assembled, differing only in that: one with a cubic pore carbon coated membrane and one with a blank membrane. The lithium deposition and extraction capacities of the two lithium copper batteries are both 2mAh/cm2The current density is 6mA/cm2. The results of the tests are similar to fig. 3, and the coulombic efficiency remained at 95.47% after 75 cycles of stabilization for the lithium copper battery using the cubic pore carbon coated separator, compared to 82.61% after 75 cycles for the lithium copper battery using the blank separator.
Example 3
(1) 1.1536g of ferric chloride and 0.4474g of manganese chloride are dissolved in a small amount (5mL) of deionized water, 7.2g of sodium gluconate is added and mixed uniformly, the mixture is heated to 80 ℃ and then is kept warm for 3h and cooled to room temperature, and a mixture of a template and a precursor is obtained;
(2) adding 80g of powdered sodium sulfate into the mixture obtained in the step (1), and fully and uniformly mixing to obtain a pre-carbonized material;
(3) heating the pre-carbonized material to 700 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 4h, and cooling to obtain a cubic pore carbon material with an inorganic salt template inside;
(4) placing the cubic pore carbon material with the inorganic salt template in dilute hydrochloric acid for 6 hours to remove the template, and cleaning and drying (drying at 100 ℃ for 24 hours) to obtain a pure cubic pore carbon material;
(5) heating the cubic pore carbon material to 900 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 4 hours, and cooling to obtain cubic pore carbon;
(6) and (3) grinding and uniformly mixing 0.6g of the cubic pore carbon obtained in the step (5) with 0.067g of PVDF binder, and coating the mixture on a PP diaphragm to obtain the cubic pore carbon coating diaphragm.
The test results are similar to those of fig. 1, and the coated separator coated carbon material prepared in this example has a nano-flake structure with cubic pores, the structure being obtained by carbonizing an organic substance and removing a template; the cubic holes are uniform in size, the side length is 25nm, and the cubic holes are closely stacked and arranged.
The test result is similar to that of FIG. 2, the contact angle of the cubic pore carbon coating diaphragm to the electrolyte is 6.8 degrees, which is smaller than that of the blank diaphragm (43.6 degrees), and the electrolyte of the cubic pore carbon coating diaphragm is completely soaked after 3 s; in contrast, the blank separator still had an electrolyte contact angle of 35.4 ° after 15 s.
Two lithium copper batteries were assembled, differing only in that: one with a cubic pore carbon coated membrane and one with a blank membrane. The lithium deposition and extraction capacities of the two lithium copper batteries are both 2mAh/cm2The current density is 6mA/cm2. The results of the tests are similar to those of fig. 3, and the coulombic efficiency remained at 95.33% after 75 cycles of stabilization for the lithium copper battery using the cubic pore carbon coated separator, compared to 82.59% after 75 cycles for the lithium copper battery using the blank separator.
Example 4
(1) 1.1536g of ferric chloride and 0.4839g of zinc chloride are dissolved in a small amount (5mL) of deionized water, 14.5g of sodium gluconate is added to be mixed uniformly, the mixture is heated to 90 ℃ and then is kept warm for 3h and cooled to room temperature, and a mixture of a template and a precursor is obtained;
(2) adding 80g of powdered sodium sulfate into the mixture obtained in the step (1), and fully and uniformly mixing to obtain a pre-carbonized material;
(3) heating the pre-carbonized material to 700 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 4h, and cooling to obtain a cubic pore carbon material with an inorganic salt template inside;
(4) placing the cubic pore carbon material with the inorganic salt template in dilute hydrochloric acid for 6 hours to remove the template, and cleaning and drying (drying at 100 ℃ for 24 hours) to obtain a pure cubic pore carbon material;
(5) heating the cubic pore carbon material to 1000 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 4h, and cooling to obtain cubic pore carbon;
(6) and (3) grinding and uniformly mixing 0.6g of the cubic pore carbon obtained in the step (5) with 0.067g of PVDF binder, and coating the mixture on a PP diaphragm to obtain the cubic pore carbon coating diaphragm.
The test results are similar to those of fig. 1, and the coated separator coated carbon material prepared in this example has a nano-flake structure with cubic pores, the structure being obtained by carbonizing an organic substance and removing a template; the cubic holes are uniform in size, the side length is 28nm, and the cubic holes are closely stacked and arranged.
The test result is similar to that of FIG. 2, the contact angle of the cubic pore carbon coating diaphragm to the electrolyte is 6.9 degrees, which is smaller than that of the blank diaphragm (43.4 degrees), and the electrolyte of the cubic pore carbon coating diaphragm is completely soaked after 3 s; in contrast, the blank separator still had an electrolyte contact angle of 35.7 ° after 15 s.
Two lithium copper batteries were assembled, differing only in that: one with a cubic pore carbon coated membrane and one with a blank membrane. The lithium deposition and extraction capacities of the two lithium copper batteries are both 2mAh/cm2The current density is 6mA/cm2. The results of the tests are similar to fig. 3, and the coulombic efficiency remained at 95.44% after 75 cycles of stabilization for the lithium copper battery using the cubic pore carbon coated separator, compared to 82.63% after 75 cycles for the lithium copper battery using the blank separator.
Example 5
(1) 1.1536g of ferric chloride and 0.4839g of zinc chloride are dissolved in a small amount (5mL) of deionized water, 10g of sodium oleate is added, the mixture is fully and uniformly mixed, the mixture is heated to 100 ℃, and then the mixture is cooled to room temperature after being kept warm for 3h, so that a mixture of a template and a precursor is obtained;
(2) adding 80g of powdered sodium sulfate into the mixture obtained in the step (1), and fully and uniformly mixing to obtain a pre-carbonized material;
(3) heating the pre-carbonized material to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, preserving heat for 3h, and cooling to obtain a cubic pore carbon material with an inorganic salt template inside;
(4) placing the cubic pore carbon material with the inorganic salt template in dilute hydrochloric acid for 6 hours to remove the template, and cleaning and drying (drying at 100 ℃ for 24 hours) to obtain a pure cubic pore carbon material;
(5) heating the cubic pore carbon material to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, preserving heat for 3h, and cooling to obtain cubic pore carbon;
(6) and (3) grinding and uniformly mixing 0.6g of the cubic pore carbon obtained in the step (5) with 0.067g of PVDF binder, and coating the mixture on a PP diaphragm to obtain the cubic pore carbon coating diaphragm.
The test results are similar to those of fig. 1, and the coated separator coated carbon material prepared in this example has a nano-flake structure with cubic pores, the structure being obtained by carbonizing an organic substance and removing a template; the cubic holes are uniform in size, the side length is 24nm, and the cubic holes are closely stacked and arranged.
The test result is similar to that of FIG. 2, the contact angle of the cubic pore carbon coating diaphragm to the electrolyte is 7.3 degrees, which is smaller than that of the blank diaphragm (43.7 degrees), and the electrolyte of the cubic pore carbon coating diaphragm is completely soaked after 3 s; in contrast, the blank separator still had an electrolyte contact angle of 35.6 ° after 15 s.
Two lithium copper batteries were assembled, differing only in that: one with a cubic pore carbon coated membrane and one with a blank membrane. The lithium deposition and extraction capacities of the two lithium copper batteries are both 2mAh/cm2The current density is 6mA/cm2. Test results similar to fig. 3, coulombic efficiency remained 95.43% after 75 weeks of stable cycling for lithium copper batteries using a cubic pore carbon coated separator, compared to lithium using a blank separatorThe coulombic efficiency dropped to 82.65% after 75 weeks of cycling for the copper cell.
Example 6
(1) 1.1536g of ferric chloride and 0.4474g of manganese chloride are dissolved in a small amount (5mL) of deionized water, 14.5g of gluconic acid is added to be fully and uniformly mixed, the mixture is heated to 70 ℃, and then the mixture is kept warm for 3h and cooled to room temperature to obtain a mixture of a template and a precursor;
(2) adding 60g of powdered sodium sulfate into the mixture obtained in the step (1), and fully and uniformly mixing to obtain a pre-carbonized material;
(3) heating the pre-carbonized material to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, preserving heat for 3h, and cooling to obtain a cubic pore carbon material with an inorganic salt template inside;
(4) placing the cubic pore carbon material with the inorganic salt template in dilute hydrochloric acid for 6 hours to remove the template, and cleaning and drying (drying at 100 ℃ for 24 hours) to obtain a pure cubic pore carbon material;
(5) heating the cubic pore carbon material to 950 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphere, preserving heat for 3 hours, and cooling to obtain cubic pore carbon;
(6) and (3) grinding and uniformly mixing 0.6g of the cubic pore carbon obtained in the step (5) with 0.067g of PVDF binder, and coating the mixture on a PP diaphragm to obtain the cubic pore carbon coating diaphragm.
The test results are similar to those of fig. 1, and the coated separator coated carbon material prepared in this example has a nano-flake structure with cubic pores, the structure being obtained by carbonizing an organic substance and removing a template; the cubic holes are uniform in size, the side length is 23nm, and the cubic holes are closely stacked and arranged.
The test result is similar to that of FIG. 2, the contact angle of the cubic pore carbon coating diaphragm to the electrolyte is 7.1 degrees, which is smaller than that of the blank diaphragm (43.5 degrees), and the electrolyte of the cubic pore carbon coating diaphragm is completely soaked after 3 s; in contrast, the blank separator still had an electrolyte contact angle of 35.8 ° after 15 s.
Two lithium copper batteries were assembled, differing only in that: one with a cubic pore carbon coated membrane and one with a blank membrane. The lithium deposition and extraction capacities of the two lithium copper batteries are both 2mAh/cm2The current density is 6mA/cm2. The results of the tests are similar to those of fig. 3, and the coulombic efficiency remained at 95.48% after 75 cycles of stabilization for the lithium copper battery using the cubic pore carbon coated separator, compared to 82.53% after 75 cycles for the lithium copper battery using the blank separator.
The properties of the cubic pore carbon material prepared in the above examples, the contact angle of the cubic pore carbon coating separator and the blank separator, and the coulomb efficiency of the assembled lithium copper battery are shown in table 1.
TABLE 1
Claims (10)
1. A coating material of a lithium metal battery coating diaphragm is characterized in that: the coating material has a nano-flake structure and is provided with cubic holes, and the cubic holes are surrounded by carbon walls;
the cubic holes are uniform in size, the side length is 20-28 nm, and the cubic holes are closely stacked and arranged.
2. The coating material of claim 1, wherein: the coating material is obtained by removing a template after carbonizing a carbon-containing organic matter;
specifically, the carbon-containing organic matter is at least one of sodium gluconate, sodium acetate and sodium oleate.
3. A method of preparing the coating material of claim 1 or 2, comprising the steps of:
(1) mixing an inorganic salt template with the carbon-containing organic matter to obtain a mixture of the template and a precursor;
(2) adding sodium sulfate into the mixture obtained in the step (1) to obtain a pre-carbonized material;
(3) heating the pre-carbonized material in an inert atmosphere to obtain a cubic pore carbon material with an inorganic salt template inside;
(4) removing the inorganic salt template from the cubic pore carbon material with the inorganic salt template inside to obtain a pure cubic pore carbon material;
(5) and (4) heating the pure cubic pore carbon material prepared in the step (4) in an inert atmosphere to obtain cubic pore carbon, namely the coating material.
4. The production method according to claim 3, characterized in that: in the step (1), the inorganic salt template is at least two of ferric chloride, manganese chloride and zinc chloride;
the molar ratio of the reaction product of the inorganic salt template to the carbon-containing organic matter is 1: 4-20;
specifically, the inorganic salt template is any one of the following: 1) ferric chloride and manganese chloride; 2) ferric chloride and zinc chloride; 3) ferric chloride, manganese chloride and zinc chloride;
more specifically, 1) ferric chloride and manganese chloride; the molar ratio of the ferric chloride to the manganese chloride is 2-5: 1; 2) ferric chloride and zinc chloride; the molar ratio of the ferric chloride to the zinc chloride is 2-5: 1; 3) ferric chloride, manganese chloride and zinc chloride; iron chloride: the molar ratio of the sum of manganese chloride and zinc chloride is 2-5: 1;
in the step (2), the molar ratio of the carbon-containing organic matter to the sodium sulfate is 1: 4-20;
in the step (2), the sodium sulfate is in a powder form.
5. The production method according to claim 3 or 4, characterized in that: in the step (3), the heating temperature is 400-700 ℃; the heat preservation time is 1-5 h;
in the step (5), the heating temperature is 800-1100 ℃; the heat preservation time is 1-5 h;
specifically, in the step (3), the heating temperature is 500-700 ℃; the heat preservation time is 3-4 h;
in the step (5), the heating temperature is 800-1000 ℃; the heat preservation time is 3-4 h.
6. The production method according to any one of claims 3 to 5, characterized in that: the step (1) further comprises the steps of heating and cooling to room temperature after mixing;
in the step (3) and the step (5), the inert atmosphere is at least one of a nitrogen atmosphere, an argon atmosphere and a helium atmosphere;
in the step (4), the cubic pore carbon material with the inorganic salt template inside is soaked in an acid solution to remove the inorganic salt template;
in the step (3), the heating rate is 1-5 ℃/min; in the step (4), the heating rate is 3-10 ℃/min.
7. A lithium metal battery coated separator comprising the coating material of claim 1 or 2 and a base film;
specifically, the base film is a PP film.
8. The method of preparing a lithium metal battery coated separator as claimed in claim 7, comprising the steps of: mixing the coating material of claim 1 or 2 with a binder, and then coating it on the base film to obtain the lithium metal battery coating separator.
9. The method of claim 8, wherein: the mass ratio of the coating material to the binder is 4-9: 1;
the binder is at least one of PVDF, PVP and PEO.
10. A lithium battery comprising the lithium metal battery coated separator of claim 7.
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