CN113851782B - High-temperature-resistant diaphragm slurry with pre-lithium supplementing function, diaphragm and lithium battery - Google Patents
High-temperature-resistant diaphragm slurry with pre-lithium supplementing function, diaphragm and lithium battery Download PDFInfo
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses high-temperature-resistant diaphragm slurry with a pre-lithium supplementing function, a diaphragm and a lithium battery, and the preparation method comprises the following steps: step 1: adding lithium aluminum titanium phosphate powder into dimethylacetamide, and uniformly dispersing to obtain a solution A; step 2: under the protection of inert gas, m-phenylenediamine is added into the solution A, after the temperature is reduced, m-phthaloyl chloride is added, calcium hydroxide is added after the temperature is gradually increased, and then dimethyl carbonate is added, so that the high-temperature-resistant diaphragm slurry with the function of pre-supplementing lithium is obtained through uniform dispersion. In the preparation process, the m-phenylenediamine and the m-phthaloyl chloride are wrapped with the titanium aluminum lithium phosphate powder in the low-temperature polymerization process, so that hydrogen bonds generated in the low-temperature polymerization process are combined with four oxygen bonds on phosphorus atoms of the titanium aluminum lithium phosphate powder to form a stable composite structure, and the high-temperature resistance of the diaphragm is greatly improved. In addition, the lithium aluminum titanium phosphate powder contained in the lithium battery can release lithium ions so as to supplement the lithium ions consumed in the electrolyte in the cycle process of the lithium battery.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms, in particular to high-temperature-resistant diaphragm slurry with a pre-lithium supplementing function, a diaphragm and a lithium battery.
Background
As new energy automobiles in the market are popular, the cruising ability of the electric car is stronger along with the development of new energy, but as the cruising ability is improved, the lithium compression energy density of the battery is higher, the safety performance of the battery is reduced, and meanwhile, the service life of the battery is shortened due to high discharge. In order to cope with such a change, it is necessary to design a power battery that can improve both the battery safety performance and the battery life.
Disclosure of Invention
The invention aims to provide high-temperature-resistant diaphragm slurry with a pre-lithium supplementing function, aiming at the technical defect that the service life of a lithium battery is shortened along with the improvement of the endurance capability in the prior art.
Another object of the present invention is to provide a high temperature resistant separator having a lithium pre-supplementing function.
Another object of the present invention is to provide a lithium battery.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a preparation method of high-temperature-resistant diaphragm slurry with a pre-lithium supplementing function comprises the following steps:
step 1: preparation of lithium aluminum titanium phosphate powder
Firstly, placing monoammonium phosphate, lithium carbonate, aluminum oxide and titanium dioxide into an oven to be dried at 150-200 ℃; the mass ratio of the monoammonium phosphate to the lithium carbonate to the alumina to the titanium dioxide is (60-65): (8-10): (2-4): (24-26); taking out, cooling, and then putting into a ball mill, grinding for 4-6 hours at 500r/min to obtain mixed powder;
then, the obtained mixed powder is put into a ceramic crucible, and then is put into a muffle furnace, and the step heating reaction is carried out to generate lithium aluminum titanium phosphate; the step heating process comprises the following steps: heating to 250-350deg.C, keeping the temperature for 2h, then continuously heating to 450-550deg.C, keeping the temperature for 2h, heating to 650-750deg.C again, keeping the temperature for 2h, and finally heating to 850-950 deg.C, keeping the temperature for 2h.
Finally, taking out and cooling to prepare a titanium aluminum lithium phosphate solid, crushing the titanium aluminum lithium phosphate, and then adding the titanium aluminum lithium phosphate solid into a ball mill to grind for 4-6 hours to obtain titanium aluminum lithium phosphate powder;
the chemical reaction equation involved in this step is:
step 2: adding the lithium aluminum titanium phosphate powder obtained in the step 1 into dimethylacetamide, wherein the mass ratio of the lithium aluminum titanium phosphate powder to the dimethylacetamide is (10-20): (80-90) uniformly dispersing to obtain a solution A;
specifically, the uniform dispersion process is that stirring is carried out for 25-45min, and then sand milling is carried out for 15-30min by a rod pin type sand mill, and the rotating speed is 500r/min.
Step 3: under the protection of inert gas, m-phenylenediamine is added into the solution A, and stirring is carried out for 20min until the m-phenylenediamine is completely dissolved, so as to obtain a solution B; cooling the solution B to 0-5 ℃, adding isophthaloyl dichloride, and stirring for 20min to obtain a solution C; gradually heating the solution C to 80 ℃ within 80min, adding calcium hydroxide, and stirring for 30min to obtain a solution D;
the chemical reaction equation involved in this step is:
the weight portion of the solution A, the weight portion of the calcium hydroxide and the proportion of the m-phenylenediamine to the total weight portion of the isophthaloyl dichloride are (78-88): (5-10): (7-12);
step 4: adding dimethyl carbonate into the solution D, stirring for 30min, and uniformly dispersing to obtain high-temperature-resistant diaphragm slurry with a lithium pre-supplementing function; the mass part ratio of the solution D to the dimethyl carbonate is (80-95): (5-20).
According to the preparation method, the m-phenylenediamine and the isophthaloyl dichloride are wrapped with the lithium aluminum titanium phosphate powder in the low-temperature polymerization process, so that hydrogen bonds generated by the m-phenylenediamine and the isophthaloyl dichloride in the low-temperature polymerization process are combined with four oxygen bonds on phosphorus atoms of the lithium aluminum titanium phosphate powder to form a stable novel composite structure, as shown in fig. 2, black parts are lithium aluminum titanium phosphate particles, and broken lines are interacted bonding positions.
In another aspect, the invention provides a high-temperature resistant diaphragm with a lithium pre-supplementing function, which comprises a base film and a coating layer formed by extracting and drying the high-temperature resistant diaphragm slurry with the lithium pre-supplementing function, wherein the coating layer is coated on two sides of the base film; the base film is a polyethylene base film, and the coating mode is anilox roller coating; the coating thickness was 1.5 μm.
The extraction is carried out by the following steps: the extraction tank is divided into 10 small tanks, the depth of each tank is 1m, the first three tanks are respectively provided with extraction liquid of deionized water and dimethylacetamide mixed according to different mass ratios, a coagulating bath is formed, the mass ratio of dimethylacetamide to water in the first tank is 3:2, the mass ratio of dimethylacetamide to water in the second tank is 1:1, the mass ratio of dimethylacetamide to water in the third tank is 2:3, the rest other tanks are respectively provided with deionized water, and a diaphragm penetrates through each tank to sequentially pass through the coagulating bath with three different concentrations and the deionized water for extraction.
In yet another aspect of the invention, a lithium battery includes a positive electrode, a negative electrode, an electrolyte, and a high temperature resistant separator having a pre-lithium supplementing function as described above.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the high-temperature-resistant diaphragm slurry with the pre-lithium supplementing function, the m-phenylenediamine and the m-phthaloyl chloride are wrapped with the titanium aluminum lithium phosphate powder in the low-temperature polymerization process, so that the hydrogen bonds generated by the m-phenylenediamine and the m-phthaloyl chloride in the low-temperature polymerization process are combined with four oxygen bonds on the phosphorus atoms of the titanium aluminum lithium phosphate powder to form a stable novel composite structure, the structure can enable the diaphragm to resist the high temperature of 200 ℃, and the high-temperature resistance of the diaphragm is greatly improved.
2. The high-temperature-resistant diaphragm slurry with the pre-lithium supplementing function, which is provided by the application, contains lithium aluminum titanium phosphate powder which can release lithium ions so as to supplement lithium ions consumed in electrolyte in the cycle process of a lithium battery.
3. According to the lithium battery provided by the invention, lithium ions consumed by the electrolyte can be timely supplemented in the charging and discharging process, so that the service life of the lithium battery is prolonged.
Drawings
Fig. 1 is a scanning electron microscope image of a high temperature resistant separator with a lithium pre-supplementing function prepared in example 1.
FIG. 2 is a schematic structural diagram of a stabilized novel composite structure.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A preparation method of high-temperature-resistant diaphragm slurry with a pre-lithium supplementing function comprises the following steps:
step 1: preparation of lithium aluminum titanium phosphate powder
Firstly, placing monoammonium phosphate, lithium carbonate, aluminum oxide and titanium dioxide into an oven to be dried at 150 ℃; the mass ratio of the monoammonium phosphate to the lithium carbonate to the alumina to the titanium dioxide is 60:8:2:24;
taking out, cooling, and then putting into a ball mill, grinding for 4 hours at 500r/min to obtain mixed powder;
then, the obtained mixed powder is put into a ceramic crucible, then is put into a muffle furnace, is heated to 250 ℃, is kept at a constant temperature for 2 hours, then is continuously heated to 450 ℃ and is kept at a constant temperature for 2 hours, is heated to 650 ℃ again, is kept at a constant temperature for 2 hours, and is finally heated to 850 ℃ and is kept at a constant temperature for 2 hours;
finally, taking out and cooling to prepare a titanium aluminum lithium phosphate solid, crushing the titanium aluminum lithium phosphate, and then adding the titanium aluminum lithium phosphate solid into a ball mill to grind for 4 hours to obtain titanium aluminum lithium phosphate powder;
step 2: adding the lithium aluminum titanium phosphate powder obtained in the step 1 into dimethylacetamide, wherein the mass ratio of the lithium aluminum titanium phosphate powder to the dimethylacetamide is 10:90, stirring for 25min, then sanding for 15min by using a rod pin type sand mill, wherein the rotating speed is 500r/min, and uniformly dispersing to obtain a solution A;
step 3: firstly, introducing nitrogen into a reaction tank for protection, adding the solution A, then adding m-phenylenediamine, and stirring for 20min until the m-phenylenediamine is completely dissolved to obtain a solution B; cooling the solution B to 0 ℃ by introducing chilled water, adding isophthaloyl dichloride, stirring for 20min to obtain a solution C, removing the chilled water, gradually heating the solution C to 80 ℃ within 80min, adding calcium hydroxide, and stirring for 30min to obtain a solution D
Wherein the ratio of the mass parts of the solution A, the mass parts of the calcium hydroxide and the total mass parts of the m-phenylenediamine and the isophthaloyl dichloride is 88:5:7; the molar ratio of the m-phenylenediamine to the isophthaloyl dichloride is 1:1;
step 4: adding dimethyl carbonate into the solution D, stirring for 30min, and uniformly dispersing to obtain high-temperature-resistant diaphragm slurry with a lithium pre-supplementing function; the mass ratio of the solution D to the dimethyl carbonate is 80:20.
And coating the high-temperature-resistant diaphragm slurry with the function of pre-supplementing lithium on two sides of a polyethylene-based film through an anilox roller, and then extracting and drying to obtain the high-temperature-resistant diaphragm with the function of pre-supplementing lithium.
The specification of the polyethylene-based film is 1000mm multiplied by 9 mu m; the gauge of the anilox roller is 1150mm multiplied by 100mm multiplied by 1.5 mu m; the coating thickness per side was 1.5 μm.
The extraction is carried out by the following steps: the extraction tank is divided into 10 small tanks, the depth of each tank is 1m, the first three tanks are respectively provided with extraction liquid of deionized water and dimethylacetamide mixed according to different mass ratios, a coagulating bath is formed, the mass ratio of dimethylacetamide to water in the first tank is 3:2, the mass ratio of dimethylacetamide to water in the second tank is 1:1, the mass ratio of dimethylacetamide to water in the third tank is 2:3, the rest other tanks are respectively provided with deionized water, and a diaphragm penetrates through each tank to sequentially pass through the coagulating bath with three different concentrations and the deionized water for extraction.
The scanning electron microscope image of the prepared high-temperature-resistant diaphragm with the function of pre-supplementing lithium is shown in fig. 1, and it can be seen from the image that the aramid fiber and the titanium aluminum lithium phosphate powder are completely combined together, the surface of the diaphragm is uniform, the powder is better in dispersion, the structure is more three-dimensional, the safety performance of the diaphragm is more improved, the net-shaped structure of the aramid fiber is more outstanding, and the aperture is more obvious, so that the lithium ions are released from the battery.
Comparative example 1
The high-temperature-resistant diaphragm slurry with the function of pre-supplementing lithium prepared in the embodiment 1 is coated on one side of a polyethylene-based film, and then the high-temperature-resistant diaphragm with the function of pre-supplementing lithium is obtained through extraction and drying. The specification of the polyethylene-based film is 1000mm×9 μm; the gauge of the anilox roller is 1150mm×100mm×1.5 μm; the coating thickness was 1.5 μm.
Comparative example 1 was a single-sided coating and other process parameters were consistent with example 1.
Example 2
A preparation method of high-temperature-resistant diaphragm slurry with a pre-lithium supplementing function comprises the following steps:
step 1: preparation of lithium aluminum titanium phosphate powder
Firstly, placing monoammonium phosphate, lithium carbonate, aluminum oxide and titanium dioxide into an oven to be dried at 180 ℃; the mass ratio of the ammonium dihydrogen phosphate to the lithium carbonate to the aluminum oxide to the titanium dioxide is 62:9:3:25;
taking out, cooling, and then putting into a ball mill to grind for 5 hours at 500r/min to obtain mixed powder;
then, the obtained mixed powder is put into a ceramic crucible, then is put into a muffle furnace, is heated to 300 ℃ and is kept at a constant temperature for 2 hours, then is continuously heated to 500 ℃ and is kept at a constant temperature for 2 hours, is heated to 700 ℃ again and is kept at a constant temperature for 2 hours, and finally is heated to 900 ℃ and is kept at a constant temperature for 2 hours;
finally, taking out and cooling to prepare a titanium aluminum lithium phosphate solid, crushing the titanium aluminum lithium phosphate, and then adding the titanium aluminum lithium phosphate solid into a ball mill to grind for 5 hours to obtain titanium aluminum lithium phosphate powder;
step 2: adding the lithium aluminum titanium phosphate powder obtained in the step 1 into dimethylacetamide, stirring for 25min, and then sanding for 25min by a rod pin type sand mill at the rotating speed of 500r/min to obtain a solution A;
step 3: firstly, introducing nitrogen into a reaction tank for protection, adding the solution A, then adding m-phenylenediamine, and stirring for 20min until the m-phenylenediamine is completely dissolved to obtain a solution B; cooling the solution B to 3 ℃ by introducing chilled water, adding isophthaloyl dichloride, stirring for 20min to obtain a solution C, removing the chilled water, gradually heating the solution C to 80 ℃ within 80min, adding calcium hydroxide, and stirring for 30min to obtain a solution D
Wherein the ratio of the mass parts of the solution A, the mass parts of the calcium hydroxide and the total mass parts of the m-phenylenediamine and the isophthaloyl dichloride is 82:9:9; the molar ratio of the m-phenylenediamine to the isophthaloyl dichloride is 1:1;
step 4: adding dimethyl carbonate into the solution D, stirring for 30min, and uniformly dispersing to obtain high-temperature-resistant diaphragm slurry with a lithium pre-supplementing function; the mass ratio of the solution D to the dimethyl carbonate is 90:10.
The high-temperature-resistant diaphragm slurry with the function of pre-lithium supplement is prepared according to the method in the embodiment 1 to obtain the high-temperature-resistant diaphragm with the function of pre-lithium supplement.
Comparative example 2
The preparation method of the high-temperature-resistant diaphragm slurry is different from that of the example 2 in that no titanium aluminum lithium phosphate powder is added, and other method parameters are consistent with those of the example 2.
The high temperature resistant membrane slurry was prepared as in example 1 to obtain a high temperature resistant membrane.
Example 3
A preparation method of high-temperature-resistant diaphragm slurry with a pre-lithium supplementing function comprises the following steps:
step 1: preparation of lithium aluminum titanium phosphate powder
Firstly, placing monoammonium phosphate, lithium carbonate, aluminum oxide and titanium dioxide into an oven to be dried at 200 ℃; the mass ratio of the monoammonium phosphate to the lithium carbonate to the alumina to the titanium dioxide is 65:10:4:26;
taking out, cooling, and then putting into a ball mill, grinding for 6 hours at 500r/min to obtain mixed powder;
then, the obtained mixed powder is put into a ceramic crucible, then is put into a muffle furnace, is heated to 350 ℃ and is kept at a constant temperature for 2 hours, then is continuously heated to 550 ℃ and is kept at a constant temperature for 2 hours, is heated to 750 ℃ again and is kept at a constant temperature for 2 hours, and finally is heated to 950 ℃ and is kept at a constant temperature for 2 hours;
finally, taking out and cooling to prepare a titanium aluminum lithium phosphate solid, crushing the titanium aluminum lithium phosphate, and then adding the titanium aluminum lithium phosphate solid into a ball mill to grind for 6 hours to obtain titanium aluminum lithium phosphate powder;
step 2: adding the lithium aluminum titanium phosphate powder obtained in the step 1 into dimethylacetamide, wherein the mass ratio of the lithium aluminum titanium phosphate powder to the dimethylacetamide is 20:80, stirring for 45min, then sanding for 30min by using a rod pin type sand mill, wherein the rotating speed is 500r/min, and uniformly dispersing to obtain a solution A;
step 3: firstly, introducing nitrogen into a reaction tank for protection, adding the solution A, then adding m-phenylenediamine, and stirring for 20min until the m-phenylenediamine is completely dissolved to obtain a solution B; cooling the solution B to 5 ℃ by introducing chilled water, adding isophthaloyl dichloride, stirring for 20min to obtain a solution C, removing the chilled water, gradually heating the solution C to 80 ℃ within 80min, adding calcium hydroxide, and stirring for 30min to obtain a solution D
Wherein the ratio of the mass parts of the solution A, the mass parts of the calcium hydroxide and the total mass parts of the m-phenylenediamine and the isophthaloyl dichloride is 78:10:12; the molar ratio of the m-phenylenediamine to the isophthaloyl dichloride is 1:1;
step 4: adding dimethyl carbonate into the solution D, stirring for 30min, and uniformly dispersing to obtain high-temperature-resistant diaphragm slurry with a lithium pre-supplementing function; the mass ratio of the solution D to the dimethyl carbonate is 95:5.
The high-temperature-resistant diaphragm slurry with the function of pre-lithium supplement is prepared according to the method in the embodiment 1 to obtain the high-temperature-resistant diaphragm with the function of pre-lithium supplement.
Comparative example 3
Comparative example 3 is different from example 3 in that the lithium aluminum titanium phosphate powder is added after the m-phenylenediamine and the isophthaloyl chloride are mixed, and the specific steps are as follows:
a method of preparing a separator slurry comprising the steps of:
step 1: preparation of lithium aluminum titanium phosphate powder
Firstly, placing monoammonium phosphate, lithium carbonate, aluminum oxide and titanium dioxide into an oven to be dried at 200 ℃; the mass ratio of the monoammonium phosphate to the lithium carbonate to the alumina to the titanium dioxide is 65:10:4:26;
taking out, cooling, and then putting into a ball mill, grinding for 6 hours at 500r/min to obtain mixed powder;
then, the obtained mixed powder is put into a ceramic crucible, then is put into a muffle furnace, is heated to 350 ℃ and is kept at a constant temperature for 2 hours, then is continuously heated to 550 ℃ and is kept at a constant temperature for 2 hours, is heated to 750 ℃ again and is kept at a constant temperature for 2 hours, and finally is heated to 950 ℃ and is kept at a constant temperature for 2 hours;
finally, taking out and cooling to prepare a titanium aluminum lithium phosphate solid, crushing the titanium aluminum lithium phosphate, and then adding the titanium aluminum lithium phosphate solid into a ball mill to grind for 6 hours to obtain titanium aluminum lithium phosphate powder;
step 2: firstly, introducing nitrogen into a reaction tank for protection, adding dimethylacetamide, then adding m-phenylenediamine, and stirring for 20min until the m-phenylenediamine is completely dissolved to obtain a solution 1; cooling the solution 1 to 5 ℃ by introducing chilled water, adding isophthaloyl dichloride, stirring for 20min to obtain a solution 2, removing the chilled water, gradually heating the solution 2 to 80 ℃ within 80min, adding calcium hydroxide, and stirring for 30min to obtain a solution 3
Wherein the ratio of the mass parts of the dimethylacetamide, the mass parts of the calcium hydroxide and the total mass parts of the m-phenylenediamine and the isophthaloyl dichloride is 82:9:9; the molar ratio of the m-phenylenediamine to the isophthaloyl dichloride is 1:1;
step 3: adding the lithium aluminum titanium phosphate powder obtained in the step 1 into dimethylacetamide, wherein the mass ratio of the lithium aluminum titanium phosphate powder to the dimethylacetamide is 20:80, stirring for 45min, then sanding for 30min by using a rod pin type sand mill, wherein the rotating speed is 500r/min, and uniformly dispersing to obtain a solution 4;
step 4: uniformly mixing the solution 3 and the solution 4, adding dimethyl carbonate, stirring for 30min, and uniformly dispersing to obtain diaphragm slurry; the mass ratio of the solution 3 to the solution 4 to the dimethyl carbonate is 40:45:15.
The high-temperature-resistant diaphragm slurry with the function of pre-lithium supplement is prepared according to the method in the embodiment 1 to obtain the high-temperature-resistant diaphragm with the function of pre-lithium supplement.
The performance parameter data of the separators prepared in the above examples and comparative examples are shown in the following table:
the shrinkage at 180 ℃ and 200 ℃ of the single-sided coated separator prepared in comparative example 1 is significantly greater than the double-sided coated separator prepared in example 1, indicating that the double-sided coating can significantly improve the high temperature resistance of the separator. This is mainly because the PE side of the single-sided coated separator will shrink and melt when passing 150 ℃ and will curl the separator towards the coated side, at which time the separator is severely deformed, resulting in an abnormally severe shrinkage, while the double-sided coating will not shrink even if reaching the melting point of PE due to the protection of the temperature-resistant coating.
The high-temperature resistant diaphragm prepared in comparative example 2 has slightly higher shrinkage at 180 ℃ and 200 ℃ than the high-temperature resistant diaphragm with the function of pre-supplementing lithium prepared in example 2, which shows that the lithium aluminum titanium phosphate powder not only can provide lithium ions, but also can be cooperated with other components in slurry to improve the high-temperature resistance of the diaphragm. The theoretical basis is that m-phenylenediamine generates more hydrogen bonds in the condensation process with isophthaloyl dichloride, and titanium aluminum lithium phosphate can form a stable novel composite structure with the hydrogen bonds between meta-aramid fibers because of four oxygen bonds on phosphorus, so that the high temperature resistance of the diaphragm is synergistically improved.
The shrinkage at 180 ℃ and 200 ℃ of the separator prepared in comparative example 3 is significantly greater than that of the high-temperature-resistant separator with the function of pre-lithium supplementation prepared in example 2. This is because m-phenylenediamine is first condensed with isophthaloyl dichloride and then added with lithium aluminum titanium phosphate powder. Four oxygen bonds on the lithium aluminum phosphate powder phosphorus cannot be combined with hydrogen bonds, and a stable composite structure cannot be formed, so that the high temperature resistance of the diaphragm is reduced.
Example 4
The separators prepared in the above examples and comparative examples were assembled to form lithium batteries in which the positive electrode was lithium iron phosphate; the negative electrode is graphite; the electrolyte takes lithium hexafluorophosphate as a solute and carbonate as a solvent. The performance parameters of the assembled lithium battery are shown in the following table:
the data show that the discharge capacity variation attenuation of the battery after 1000 cycles in examples 1-3 is very small, which proves that the lithium battery assembled by the high-temperature-resistant diaphragm with the function of pre-lithium supplement of the invention can effectively improve the capacity retention rate of the battery in the cycle process. In comparative example 1, although the effect of lithium pre-charging was achieved by single-sided coating, the battery life could not be effectively improved because of the less charging. In comparative example 2, without lithium aluminum titanium phosphate, lithium ion decay in the battery cannot be pre-compensated, resulting in faster energy decay. Comparative example 3 because of the different doping forms of the lithium aluminum titanium phosphate powder, the efficiency of releasing lithium ions is lower, resulting in slower speed of pre-lithium supplementation.
By adjusting the process parameters according to the present disclosure, the high temperature resistant separator slurry with a lithium pre-supplementing function of the present disclosure can be prepared and exhibits substantially the same performance as in example 1.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A preparation method of high-temperature-resistant diaphragm slurry with a pre-lithium supplementing function is characterized by comprising the following steps of: the method comprises the following steps:
step 1: adding lithium aluminum titanium phosphate powder into dimethylacetamide, and uniformly dispersing to obtain a solution A;
step 2: under the protection of inert gas, m-phenylenediamine is added into the solution A, and the mixture is stirred until the m-phenylenediamine is completely dissolved to obtain a solution B; cooling the solution B, adding m-phthaloyl chloride, and stirring to obtain a solution C; gradually heating the solution C, adding calcium hydroxide, and stirring to obtain a solution D;
the m-phenylenediamine and the m-phthaloyl chloride are wrapped with lithium aluminum titanium phosphate powder in the low-temperature polymerization process, so that hydrogen bonds generated in the low-temperature polymerization process of the m-phenylenediamine and the m-phthaloyl chloride are combined with four oxygen bonds on phosphorus atoms of the lithium aluminum titanium phosphate powder;
step 3: and adding dimethyl carbonate into the solution D, and uniformly dispersing to obtain the high-temperature-resistant diaphragm slurry with the function of pre-supplementing lithium.
2. The method of manufacturing according to claim 1, wherein: in the step 1, the preparation method of the lithium aluminum titanium phosphate powder comprises the following steps of,
firstly, drying monoammonium phosphate, lithium carbonate, aluminum oxide and titanium dioxide at 150-200 ℃; the mass ratio of the monoammonium phosphate to the lithium carbonate to the alumina to the titanium dioxide is (60-65): (8-10): (2-4): (24-26); grinding for 4-6h after cooling to obtain mixed powder;
then, the obtained mixed powder undergoes a step heating reaction to generate lithium aluminum titanium phosphate; the step heating process comprises the following steps: heating to 250-350deg.C, keeping the temperature for 2h, then continuously heating to 450-550deg.C, keeping the temperature for 2h, heating to 650-750deg.C again, keeping the temperature for 2h, and finally heating to 850-950 deg.C, keeping the temperature for 2h;
and finally, taking out and cooling to prepare a titanium aluminum lithium phosphate solid, crushing the titanium aluminum lithium phosphate, and grinding for 4-6 hours to obtain titanium aluminum lithium phosphate powder.
3. The method of manufacturing according to claim 1, wherein: in the step 1, the mass ratio of the lithium aluminum titanium phosphate powder to the dimethylacetamide is (10-20): (80-90).
4. A method of preparation as claimed in claim 3, wherein: in the step 1, the uniform dispersion process is that stirring is carried out for 25-45min, and then sand milling is carried out for 15-30min by a rod pin type sand mill, wherein the rotating speed is 500r/min.
5. The method of manufacturing according to claim 1, wherein: in the step 2, the ratio of the mass parts of the solution A, the mass parts of the calcium hydroxide and the total mass parts of the m-phenylenediamine and the m-phthaloyl chloride is (78-88): (5-10): (7-12); the molar ratio of m-phenylenediamine to isophthaloyl dichloride is 1:1.
6. The method of manufacturing according to claim 1, wherein: in the step 3, the mass part ratio of the solution D to the dimethyl carbonate is (80-95): (5-20).
7. The high-temperature-resistant diaphragm slurry with the function of pre-supplementing lithium prepared by the preparation method of any one of claims 1-6.
8. The high-temperature-resistant diaphragm with the function of pre-lithium supplementation, which is characterized by comprising a base film and a coating layer formed by the high-temperature-resistant diaphragm slurry with the function of pre-lithium supplementation, which is coated on two sides of the base film, according to claim 7.
9. The high temperature resistant separator with a pre-lithium supplementing function according to claim 8, wherein said base film is a polyethylene-based film;
the coating mode is anilox roller coating.
10. A lithium battery, comprising a positive electrode, a negative electrode, an electrolyte and the high-temperature resistant separator with the function of pre-supplementing lithium according to claim 9.
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| CN115275522B (en) * | 2022-09-27 | 2023-03-24 | 宁德卓高新材料科技有限公司 | Lithium-supplementing diaphragm and preparation method and application thereof |
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