CN115799610A - Composite membrane and preparation method thereof, PVDF microporous membrane wrapping lithium salt grafted carbon nanotube and solid-state battery - Google Patents
Composite membrane and preparation method thereof, PVDF microporous membrane wrapping lithium salt grafted carbon nanotube and solid-state battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a composite film, which comprises the following steps: adding the lithium salt grafted carbon nano tube into a solvent to form a first suspension, and dispersing; adding PVDF powder, PMMA powder and an auxiliary agent into the first suspension, and heating to prepare first slurry; feeding a substrate into a coating device, and coating the surface of the substrate by using the first slurry; and drying and rolling the coated substrate to obtain the composite membrane of the PVDF microporous membrane containing the lithium salt grafted carbon nanotubes. Compared with the electrolyte membrane without the carbon nano tube, the electrolyte membrane prepared by the method has the advantages that the lithium ion conductivity is greatly improved, and meanwhile, the capacity of the solid-state battery prepared by the method after being cycled for 2000 times is improved by 50 percent compared with the solid-state battery using the PVDF microporous membrane without the carbon nano tube, and the energy density is greatly improved.
Description
Technical Field
The invention relates to the technical field of solid batteries, in particular to a composite membrane, a preparation method thereof, a PVDF microporous membrane wrapping lithium salt grafted carbon nanotubes and a solid battery.
Background
At present, electric automobiles develop rapidly, the annual growth rate increases year by year, countries release the time for selling fuel oil automobiles prohibited, and the battery system of the electric automobiles is particularly important, the electric automobiles on the market are mainly lithium batteries at present, but the lithium batteries at present have the problems of low energy density, large volume, low safety coefficient and low charging and discharging speed, and the existing solid batteries generally use an adhesive layer and the like to replace a diaphragm as a scheme for improving the problems, but the simple adhesive layer has low heat resistance and low ionic conductivity, and can reduce the passing rate of ions in the adhesive, so that the safety, the energy density and the charging and discharging efficiency of the batteries are influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a PVDF microporous membrane wrapping lithium salt grafted carbon nanotubes, the PVDF microporous membrane and a solid-state battery, which solve one or more of the problems in the prior art.
In one aspect, the present invention provides a method for preparing a composite film, comprising the steps of:
adding the lithium salt grafted carbon nano tube into a solvent to form a first suspension, and dispersing;
adding PVDF powder, PMMA powder and an auxiliary agent into the first suspension, and heating to prepare first slurry;
feeding a substrate into a coating device, and coating the surface of the substrate by using the first slurry;
and drying and rolling the coated substrate to obtain the composite membrane of the PVDF microporous membrane containing the lithium salt grafted carbon nanotubes.
Compared with the PVDF layer used in the existing solid battery, the PVDF composite material is prepared by adding PMMA powder and lithium salt grafted carbon nanotubes into the PVDF powder, mixing and coating the mixture on the base material, so that the heat resistance and the ionic conductivity of the PVDF composite material are better improved when the PVDF composite material is applied to the solid battery.
In some embodiments, the PVDF powder: the weight ratio of the PMMA powder is 5 to 1-10: the PVDF powder is 1.
In some embodiments, the substrate is a PET film, BOPP film, PVC film.
In some embodiments, before the step of adding the lithium salt-grafted carbon nanotubes to the solvent to form the first suspension for dispersion, the method comprises the following steps:
adding a carbon nanotube into mixed acid, wherein the mixed acid comprises concentrated sulfuric acid and concentrated nitric acid with a molar ratio of 1 to 4, and heating to 60 to 100 ℃ for reflux stirring reaction;
filtering to obtain an intermediate product;
washing the intermediate product with pure water for many times until the pH value of the washed pure water is 3 to 4, and then drying the intermediate product through an oven to obtain the completely carboxylated carbon nanotube;
adding the completely carboxylated carbon nano tube and lithium salt into a pure water solvent to form a second suspension, and performing ultrasonic dispersion;
drying the carbon nanotubes by an oven, and grinding the carbon nanotubes into powder to obtain the lithium salt grafted carbon nanotubes.
In some embodiments, the solvent is one or more of acetone or N-methylpyrrolidone.
In some embodiments, the step of adding a lithium salt to the solvent further comprises mixing the lithium salt-grafted carbon nanotubes with a dispersant.
In some embodiments, the step of adding a lithium salt to the solvent to form a first suspension and dispersing further comprises mixing the lithium salt grafted carbon nanotubes with a dispersant.
Preferably, the first suspension comprises
5 to 10 parts of lithium salt grafted carbon nano tube;
0.5 to 2 parts of a dispersant;
and 100 parts of an organic solvent.
In some embodiments, the dispersant is one or more of an alkali metal phosphate or an organic dispersant.
In some embodiments, the alkali metal phosphate comprises at least one of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate, and the organic dispersant comprises at least one of triethylhexylphosphoric acid, sodium dodecyl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, and polyethylene glycol fatty acid ester.
In some embodiments, the adjuvant comprises a cross-linking agent and/or a defoaming agent.
In some embodiments, the cross-linking agent is one or more of polyethylene glycol or polyethylene oxide, and the defoamer is one or more of silicone emulsion, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane, and the like.
It can be understood that the addition of the auxiliary agent in the system can make the raw materials in the slurry system have better compatibility, dispersibility and uniformity, and can make the film better in the subsequent coating film-making process.
In some embodiments, in the step of heating to obtain the first slurry, the heating temperature is 50 to 80 ℃, and the heating time is 3 to 6 hours.
In some embodiments, the heating process further comprises a stirring step.
In some embodiments, the coating step using the first slurry is performed by one of dip coating, spray coating, doctor blade, coating wire bar, and micro-gravure coating.
In some embodiments, the PVDF film coated on the substrate has a thickness of 10 to 20 μm.
In some embodiments, the step of drying the coated substrate further comprises a step of washing with water. It can be understood that the step of washing before the substrate drying step can not only achieve the purpose of pore-forming, but also improve the production efficiency, and simultaneously give consideration to the environmental protection and the safety in the production process. In other embodiments, the pores may be formed directly after the solvent in the slurry is evaporated during the drying process without water washing.
In some embodiments, in the step of drying the coated substrate, the drying temperature is 100 to 150 ℃ and the drying time is 10 to 120min.
On the other hand, the invention provides a composite membrane which comprises a base material and a PVDF microporous membrane and is prepared by adopting the method.
On the other hand, the invention provides a PVDF microporous membrane wrapping lithium salt grafted carbon nanotubes, which is obtained by stripping the composite membrane prepared by the method.
In still another aspect, the present invention provides a solid-state battery characterized by comprising
An electrolyte membrane;
the electrolyte membrane adopts the PVDF microporous membrane which is prepared by the preparation method and is obtained by stripping the composite membrane from the base material.
Drawings
Fig. 1 is a capacity cycling graph of the solid-state batteries prepared in example 1 and comparative example 1.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are only for illustrating the performance of the present invention more clearly and are not limited to the following examples.
Example 1
Weighing 0.5g of carbon nano tube, putting the carbon nano tube into a three-neck flask, adding 200ml of concentrated sulfuric acid and 100ml of concentrated nitric acid, heating to 60 ℃, carrying out reflux stirring reaction at the stirring speed of 30rmb/min for 10h, washing for 3 times by using pure water until the pH value is 3-4, then putting the carbon nano tube into a drying box at the temperature of 80 ℃, and drying for 24h to obtain the carboxylated carbon nano tube.
Then 0.5g of carboxylated carbon nanotube is weighed and placed in a beaker, 2g of lithium perchlorate (LiClO 4) is added in the beaker, 300g of pure water is poured in and uniformly stirred, the mixture is heated to 20 ℃, ultrasonically dispersed for 180min, then the mixture is placed in an oven at 120 ℃ for drying for 12h, and then the dried mixture is ground by a mortar for 10min to powder, so as to obtain the lithium salt grafted carbon nanotube.
Adding 500g of lithium salt grafted carbon nano tube prepared by the preparation method into a stirring tank, then adding 5% of dispersing agent, pouring 100L of NMP solvent, stirring for 30min, after the dispersion is finished, pouring 20kg of PVDF powder, 2kg of PMMA and 0.5kg of PEG, adding 0.5kg of defoaming agent, heating to 50 ℃, stirring at the speed of 60rmb/min, and stirring for 6h to prepare slurry.
On a single-side coating machine, a PET film is used as a substrate, a gravure roll coating process is used, the coating thickness is 10 microns, NMP is washed away through a water washing process, then the NMP is dried through a drying oven at 100 ℃, PVDF solution is solidified into a membrane, the membrane and PET are wound into a coiled material, and the carbon nano tube composite PVDF film is obtained.
Example 2
Weighing 2g of carbon nano tube, putting the carbon nano tube into a three-neck flask, adding 300ml of concentrated sulfuric acid and 300ml of concentrated nitric acid, heating to 100 ℃, carrying out reflux stirring reaction at a stirring speed of 50rmb/min for 5 hours, washing for 3 times by using pure water until the PH value is 3-4, then putting the carbon nano tube into a drying box at 120 ℃, and drying for 12 hours to obtain the carboxylated carbon nano tube.
Then weighing 2g of carboxylated carbon nanotube and placing the carboxylated carbon nanotube into a beaker, adding 8g of lithium tetrafluoroborate (LiBF 4) into the beaker, pouring 500g of pure water, uniformly stirring, heating to 60 ℃, ultrasonically dispersing for 60min, then placing the mixture into an oven at 120 ℃ for drying for 24h, and then grinding the dried mixture into powder by using a mortar for 10min to obtain the lithium grafted carbon nanotube.
3000g of lithium salt grafted carbon nano tube prepared by the preparation method is added into a stirring tank, then 10% of dispersing agent is added, 100L of NMP solvent is poured, stirring is carried out for 60min, after the dispersion is finished, 20kg of PVDF powder, 4kg of PMMA and 2kg of PEO are poured, 2kg of defoaming agent is added, the temperature is increased to 80 ℃, the stirring speed is 30rmb/min, and stirring is carried out for 3h, so that slurry is prepared.
On a single-side coating machine, a PET film is used as a substrate, a gravure roll coating process is used, the coating thickness is 20 microns, NMP is washed away through a water washing process, then drying is carried out through a drying oven at 150 ℃, PVDF solution is solidified into a membrane, the membrane and PET are wound into a coiled material, and the carbon nano tube composite PVDF film is obtained.
Example 3
Weighing 1g of carbon nano tube, putting the carbon nano tube into a three-neck flask, adding 2000ml of concentrated sulfuric acid and 500ml of concentrated nitric acid, heating to 80 ℃, carrying out reflux stirring reaction at the stirring speed of 40rmb/min for 8 hours, washing for 3 times by using pure water until the PH value is 3-4, then putting the carbon nano tube into a drying box at the temperature of 100 ℃, and drying for 18 hours to obtain the carboxylated carbon nano tube.
Then weighing 1g of carboxylated carbon nanotube and placing the weighed carboxylated carbon nanotube into a beaker, adding 6g of lithium hexafluorophosphate (LiPF 6) into the beaker, pouring 400g of pure water, uniformly stirring, heating to 40 ℃, ultrasonically dispersing for 120min, then placing the mixture into an oven at 120 ℃ for drying for 18h, and then grinding the dried product into powder by using a mortar for 10min to obtain the lithium grafted carbon nanotube.
2000g of lithium salt grafted carbon nano tube prepared by the preparation method is added into a stirring tank, then 10% of dispersing agent is added, 100L of NMP solvent is poured, stirring is carried out for 40min, after the dispersion is finished, 20kg of PVDF powder, 3kg of PMMA, 1kg of mixture of PEG and PEO are poured, 1kg of defoaming agent is added, the temperature is raised to 60 ℃, the stirring speed is 40rmb/min, and stirring is carried out for 4h, so that slurry is prepared.
On a single-side coating machine, a PET film is used as a substrate, a gravure roll coating process is used, the coating thickness is 15 micrometers, NMP is washed away through a water washing process, then drying is carried out through a drying oven at 120 ℃, PVDF solution is solidified into a membrane, the membrane and PET are wound into a coiled material, and the carbon nano tube composite PVDF film is obtained.
Comparative example 1:
on a single-side coating machine, a PET film is used as a substrate, a gravure roll coating process is used, the coating thickness is 10 micrometers, then the PET film is dried by an oven at 120 ℃, a PVDF solution is solidified into a film, and the film and the PET are wound into a coiled material to obtain the PVDF film.
Peeling the base material of the composite film prepared in the embodiment 1 and the composite film prepared in the comparative example 1 from a PVDF film to obtain a PVDF electrolyte membrane coated with a lithium salt grafted carbon nano tube, preparing the PVDF electrolyte membrane and a positive electrode and a negative electrode into a soft package battery, carrying out hot pressing at the temperature of 60-90 ℃ under the pressure of 500kg-3 t, and then testing the cycle number and the capacity retention rate of the battery, and the energy density and the safety of high-temperature tests.
The electrolyte membrane was tested and the results are shown in table 1:
| electrolyte membrane sheet obtained in comparative example 1 | Electrolyte membrane obtained in example 1 | Electrolyte membrane obtained in example 2 | Electrolyte membrane sheet obtained in example 3 | |
| Heat shrinkage at 180 deg.C for 1h | Melting | 5.8% | 1.8% | 3.2% |
| Conductivity of lithium ion | Is not conductive | 1.35*10-4 S/cm | 2.52*10-2S/cm | 3.76*10-3 S/cm |
| Tensile strength | 43Mpa | 84Mpa | 134Mpa | 103Mpa |
Table 1: test results of electrolyte membranes
The solid-state batteries prepared in example 1 and comparative example 1 were subjected to test reliability tests, and the test results are shown in table 2:
| solid-state battery based on comparative example 1 | Solid-state battery based on example 1 | |
| Capacity after 2000 |
60% | 90% |
| High temperature testing | No short circuit at 120 deg.C | No short circuit at 180 DEG C |
| Energy density | 200 Wh/KG | 350~400Wh/KG |
Table 2: test results of solid-state batteries
From the test results, it can be seen that:
compared with the electrolyte membrane of the comparative example 1, the electrolyte membrane of the example 1 has greatly improved lithium ion conductivity, the capacity of the solid-state battery prepared in the example 1 after 2000 cycles is improved by 30% compared with the solid-state battery of the comparative example 1, and the energy density is greatly improved.
Therefore, the composite carbon nanotube in the embodiment of the present application has a one-dimensional structure, the carbon nanotube is fully carboxylated by an oxidation method, the inner wall and the port of the carbon nanotube are covered by carboxyl functional groups, and then lithium salts are grafted in the tube wall and the port to ensure that electrons cannot pass through the inside of the nanotube, but the lithium salts can be transmitted through the ions.
The above description is only a preferred form of the invention, and it should be noted that it is possible for a person skilled in the art to make several variations and modifications without departing from the inventive concept, and these should also be considered as within the scope of the invention.
Claims (13)
1. A method for preparing a composite membrane, comprising the steps of:
adding the lithium salt grafted carbon nano tube into a solvent to form a first suspension, and dispersing;
adding PVDF powder, PMMA powder and an auxiliary agent into the first suspension, and heating to prepare first slurry;
feeding a substrate into a coating device, and coating the surface of the substrate by using the first slurry;
drying and rolling the coated substrate to obtain the composite membrane of the PVDF microporous membrane containing the lithium salt grafted carbon nanotubes;
preferably, the PVDF powder: the weight ratio of the PMMA powder is 5 to 1-10: the PVDF powder is 1;
preferably, the base material is a PET film, a BOPP film or a PVC film.
2. The method of claim 1, wherein prior to the step of adding the lithium salt-grafted carbon nanotubes to the solvent to form the first suspension for dispersion, the method comprises the steps of:
adding a carbon nanotube into mixed acid, wherein the mixed acid comprises concentrated sulfuric acid and concentrated nitric acid with a molar ratio of 1 to 4, and heating to 60 to 100 ℃ for reflux stirring reaction;
filtering to obtain an intermediate product;
washing the intermediate product with pure water for many times until the pH value of the washed pure water is 3 to 4, and then drying the intermediate product through an oven to obtain the completely carboxylated carbon nanotube;
adding the completely carboxylated carbon nano tube and lithium salt into a pure water solvent to form a second suspension, and performing ultrasonic dispersion;
drying the carbon nanotubes by an oven, and grinding the carbon nanotubes into powder to obtain the lithium salt grafted carbon nanotubes.
3. The method of claim 1, wherein the solvent is one or more of acetone or N-methylpyrrolidone.
4. The method of claim 1, wherein the step of adding a lithium salt grafted carbon nanotube to a solvent to form a first suspension and dispersing further comprises mixing the lithium salt grafted carbon nanotube with a dispersant.
Preferably, the first suspension comprises
5 to 10 parts of lithium salt grafted carbon nano tube;
0.5 to 2 parts of a dispersant;
and 100 parts of an organic solvent.
5. The preparation method according to claim 4, characterized in that the dispersant is one or more of alkali metal phosphate or organic dispersant; preferably, the alkali metal phosphate comprises at least one of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate, and the organic dispersant comprises at least one of triethylhexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum and fatty acid polyglycol ester.
6. The preparation method according to claim 1, wherein the auxiliary agent comprises a cross-linking agent and/or a defoaming agent, preferably, the cross-linking agent is one or more of polyethylene glycol or polyethylene oxide, and the defoaming agent is one or more of silicone emulsion, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane, and the like.
7. The method for preparing the first slurry according to claim 1, wherein the heating is performed at a temperature of 50 to 80 ℃ for 3 to 6 hours, and preferably, the heating process further comprises a stirring step.
8. The production method according to claim 1, wherein in the coating step using the first slurry, the coating means is one of dip coating, spray coating, a doctor blade, a wire bar, and micro gravure coating, and preferably, the thickness of the coating film is 10 to 20 μm.
9. The method of claim 1, further comprising a water washing step before the drying step of the coated substrate.
10. The method according to claim 1, wherein in the step of drying the coated substrate, the drying temperature is 100 to 150 ℃ and the drying time is 10 to 120min.
11. A composite membrane, which is characterized by comprising a base material and a PVDF microporous membrane, and is prepared by the method of any one of claims 1 to 10.
12. The PVDF microporous membrane wrapping the lithium salt grafted carbon nanotube is characterized by being obtained by stripping from a composite membrane prepared by the method of any one of claims 1 to 10.
13. A solid-state battery characterized by comprising
An electrolyte membrane;
the electrolyte membrane is a PVDF microporous membrane after peeling a substrate from a composite membrane produced by the production method according to any one of claims 1 to 10.
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