CN116444261A - Lithium metaaluminate material and preparation method and application thereof - Google Patents
Lithium metaaluminate material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 84
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 78
- 238000000498 ball milling Methods 0.000 claims abstract description 49
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 29
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 15
- 238000005524 ceramic coating Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 102220065682 rs77311724 Human genes 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 36
- 239000000919 ceramic Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000010902 jet-milling Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a lithium metaaluminate material, which comprises the following steps: s1, mixing lithium carbonate with nano-scale aluminum oxide, uniformly ball-milling, sintering at 530-725 ℃ for 6-9.5 hours, and then sintering at 730-860 ℃ for 2.5-4.5 hours to obtain a sintered material A; s2, crushing the sintering material A, carrying out hydrogenation treatment, standing for a period of time, carrying out solid-liquid separation, washing the obtained solid substance, and drying and crushing to obtain powder B; s3, sintering the powder B at 930-965 ℃ for 45-65min to obtain the composite material. The lithium metaaluminate ceramic material disclosed by the invention is coated by the diaphragm, so that the structural stability of the diaphragm at high temperature can be effectively improved, the safety of a battery is ensured, the lithium ion transmission rate can be effectively improved, and the lithium metaaluminate ceramic material is suitable for long-term use under the condition of high-rate charge and discharge.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium metaaluminate material and a preparation method and application thereof.
Background
The application of the lithium ion battery at present has been extended to the aspects of human life, and clean and convenient energy is brought to people. In particular, the application of lithium ion batteries in the power market is more and more extensive, and the industrial sales volume is increased year by year. The lithium battery is first used in the digital field since the birth, which mainly uses the high energy density characteristic of the lithium ion battery, and the main application market is the market of mobile phones, portable power supplies and the like, and the research and application of improving the multiplying power performance are not promoted greatly because the application market does not need the large multiplying power performance. The application of the lithium ion battery in the electric market promotes the research of the high-rate characteristic of the lithium ion battery, and in order to improve the power density of the battery output, researchers develop a series of researches from different angles such as material preparation, processing and manufacturing, formula improvement, diaphragm improvement and the like, so that a lot of great progress is made. Particularly in the aspect of diaphragm improvement, german BMW and Benz successively push out superconducting diaphragms, and particularly nanoscale aluminum oxide is adopted to carry out coating operation on the surface of a PE diaphragm, so that the superconducting characteristic of a battery diaphragm is realized, the high-rate characteristic of the battery during working is ensured, and the output power of a power battery is ensured to be capable of rapidly driving the high-power output of a motor. From the proposal of the 2008 superconducting diaphragm concept, the diaphragm industry in China expands a series of researches, the diaphragm coating materials which are used in batches in the market at present are alumina and zirconia ceramics, and the ceramic diaphragm prepared by coating the alumina and zirconia ceramics on the surface of a polymer diaphragm can effectively improve the charge-discharge rate performance of a battery, so that the industry derives a quick-charging battery, effectively solves the defect of slow charging of an electric automobile, and simultaneously solves the climbing problem and the hundred kilometers acceleration problem of the electric automobile. The application of the ceramic diaphragm rapidly expands the application field of lithium ion batteries, and the birth of electric ships, electric yachts, electric sports cars, high-speed motorcycles, electric trucks and electric lifting vehicles is possible, thereby developing a brand-new application field.
The zirconia and alumina ceramic diaphragms used in the market at present can effectively realize the continuous charge and discharge performance of 1C, and can effectively meet the market demands of electric automobiles and electric two-wheeled vehicles. However, in the application markets of electric tools, weightlifting equipment, trucks and the like, the service time of the battery can be shortened seriously in the high-rate charging and discharging process due to the limitation of the rate performance of the lithium battery, and the battery performance is deteriorated rapidly. Therefore, it is necessary to further research and develop ceramic materials and diaphragms having more excellent performance on the basis of the existing ceramic diaphragms.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the lithium metaaluminate material, the preparation method and the application thereof, and the prepared lithium metaaluminate ceramic material is coated by a diaphragm, so that the structural stability of the diaphragm at high temperature can be effectively improved, the safety of a battery can be ensured, the lithium ion transmission rate can be effectively improved, and the lithium metaaluminate ceramic material is suitable for long-term use under the condition of high-rate charge and discharge.
The invention provides a preparation method of a lithium metaaluminate material, which comprises the following steps:
s1, mixing lithium carbonate with nano-scale aluminum oxide, uniformly ball-milling, sintering at 530-725 ℃ for 6-9.5 hours, and then sintering at 730-860 ℃ for 2.5-4.5 hours to obtain a sintered material A;
s2, crushing the sintering material A, carrying out hydrogenation treatment, standing for a period of time, carrying out solid-liquid separation, washing the obtained solid substance, and drying and crushing to obtain powder B;
s3, sintering the powder B at 930-965 ℃ for 45-65min to obtain the composite material.
In S1, sintering is carried out for 6-9.5 hours at 530-725 ℃ to enable evenly dispersed lithium carbonate particles to be melted to form tiny liquid drops, the tiny liquid drops infiltrate into aluminum oxide particles in the melting process, meanwhile, lithium metaaluminate crystal nuclei are formed, the mutual infiltration of lithium carbonate and aluminum oxide is ensured to be sufficient through long-time sintering, the crystal nuclei continuously grow, the crystal forms are complete, the crystals are pure, and the ion transmission performance is better; the purpose of sintering at 730-860 ℃ for 2.5-4.5 hours is to fully decompose lithium carbonate and react with aluminum oxide to generate lithium metaaluminate.
Preferably, in S1, the temperature is raised to 530-725 ℃ at a temperature rise rate of 5-7 ℃/min, the temperature is kept for sintering for 6-9.5h, then the temperature is raised to 730-860 ℃ at a temperature rise rate of 5-7 ℃/min, and the temperature is kept for sintering for 2.5-4.5h.
Preferably, the molar ratio of lithium carbonate to nanoscale aluminum oxide is (1-1.05): 1.
preferably, the granularity of the lithium carbonate is 3-60 mu m, and the purity is 99.9% -99.999%; the granularity of the nano-scale aluminum oxide is 20-65nm, and the purity is 99-99.9%.
Among them, the nano-sized aluminum oxide may be commercially available or prepared through a conventional method such as a vapor deposition method, a plasma deposition method, a solid phase method, a pyrolysis method, a liquid phase deposition method, or a precipitation method.
Preferably, in S1, the ball milling is dry ball milling or wet ball milling.
Preferably, the conditions of the dry ball milling are as follows: ball-material ratio is 1:1-1:1.3, ball milling time is 2.5-4h, ball matching ratio is R3:R5:R10:R20=5:3:1:1, and rotating speed is 25-28R/min.
Preferably, the conditions of the wet ball milling are as follows: ball material ratio is 1:1-1:1.3, ball milling time is 2.5-4h, ball matching ratio is R3:R5:R10:R20=5:3:1:1, rotating speed is 25-28R/min, ball milling solvent is water, and water consumption is 15-30% of the sum of mass of lithium carbonate and aluminum oxide. Wherein, when wet ball milling is adopted, drying treatment is also needed after ball milling is finished.
Preferably, in S2, the specific step of performing the hydrogenation treatment includes: deionized water is added into a hydrogenation device, and CO is continuously introduced from the bottom of the hydrogenation device 2 Continuously introducing CO into the gas for 10-15min 2 Slowly adding the materials obtained by crushing the sintering material A under the condition of gas, and continuously introducing CO under the stirring 2 The hydrogenation reaction is carried out for 45-90 min. The purpose of the hydrogenation treatment is to enable impurities such as lithium carbonate, lithium oxide, lithium hydroxide and the like in the materials to generate lithium bicarbonate through hydrogenation reaction, and then the lithium bicarbonate is removed through solid-liquid separation and washing, so that the effect of removing impurities is achieved.
In S2, the purpose of standing is to effectively dissolve lithium bicarbonate generated by hydrogenation reaction and ensure impurity removal effect. Preferably, in S2, the time of rest is 4-6 hours.
Preferably, in S2, CO 2 The flow rate of the gas is 3-8L/min.
Preferably, in S2, the hydrogenation is carried out with stirring at a speed of 15-25r/min.
Preferably, in S2, the solid-to-liquid ratio of the hydrogenation reaction is 1:20-23.
In S3, sintering is carried out at 930-965 ℃ for 45-65min to ensure that lithium metaaluminate is completely converted from a metastable state into a steady state, and the crystal form conversion of a coating on a storage, use, film coating process and finished diaphragm is avoided. .
Preferably, in S3, the temperature is raised to 930-965 ℃ at a temperature rise rate of 5-7 ℃/min, and the sintering is carried out for 45-65min.
Preferably, in S3, after sintering is completed, the method further includes: and cooling the material obtained by sintering, and crushing to submicron level.
A lithium metaaluminate material is prepared by the preparation method.
The lithium metaaluminate material is applied as a lithium ion battery diaphragm coating material.
A lithium ion battery separator comprising a base film and a ceramic coating coated on at least one side surface of the base film, the ceramic coating comprising the lithium metaaluminate material.
Preferably, the mass of the lithium metaaluminate material accounts for 97.5-98% of the mass of the ceramic coating.
Preferably, the ceramic coating further comprises a binder; preferably, the mass of the binder accounts for 2-2.5% of the mass of the ceramic coating; preferably, the binder is a PVDF binder.
Preferably, the thickness of one side of the ceramic coating is 1-2 μm; preferably, the base film is a PE base film.
The beneficial effects of the invention are as follows:
according to the invention, high-purity lithium carbonate and aluminum oxide are used as raw materials, and the three-step sintering and hydrogenation are performed to remove impurities, so that the prepared lithium metaaluminate ceramic material has the characteristics of high purity and stable structure, has stronger transmission performance on lithium ions, can realize the superconducting property of a battery diaphragm by coating the lithium metaaluminate ceramic material on a lithium ion battery diaphragm base film, can improve the charge-discharge rate performance of the battery, can effectively improve and maintain the capacity of the battery, and can permanently maintain the cycle performance and the rate performance in a long-cycle process; in addition, as the chemical property of the lithium metaaluminate is stable, the high-temperature safety performance of the lithium ion power battery can be effectively ensured.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Preparing a lithium metaaluminate material:
s1, adding 740g of lithium carbonate with the purity of 99.999 percent and the granularity of 3-15 mu m and 1020g of nano-grade aluminum oxide with the purity of 99.9 percent and the granularity of 20nm into a ball milling tank made of aluminum oxide, ball milling for 2.5 hours under the conditions that the ball weight ratio is 1:1, the ball distribution ratio is R3:R5:R 10:R20=5:3:1:1 and the ball milling tank rotating speed is 25R/min, after ball milling, firstly heating to 715 ℃ in a sintering furnace at the heating rate of 5 ℃/min, preserving heat, sintering for 7.5 hours, then heating to 830 ℃ at the heating rate of 5 ℃/min, preserving heat, sintering for 3 hours, and cooling to room temperature along with the furnace to obtain a sintering material A;
s2, adding deionized water into the hydrogenation tank, and continuously introducing CO from the bottom of the hydrogenation tank 2 The gas is continuously introduced into CO for 10min (the gas flow rate is 5L/min) 2 Slowly adding the material obtained by crushing the sintering material A under the condition of gas, wherein the weight ratio of the material obtained by crushing the sintering material A to deionized water is 1:20, and continuously introducing CO under the stirring condition of 25r/min 2 The gas reacts for 45min, and then CO is stopped being introduced 2 Standing for 6h, centrifugally separating, washing the obtained precipitate with deionized water for 3 times, drying, and pulverizing to obtain powder B;
and S3, heating the powder B to 930 ℃ in a sintering furnace at a heating rate of 5 ℃, preserving heat and sintering for 60min, cooling to room temperature, and then performing jet milling to submicron order.
Preparing a ceramic diaphragm:
mixing the prepared lithium metaaluminate material with a binder PVDF according to a ratio of 98:2, adding NMP solvent, mixing uniformly to obtain slurry, uniformly coating on one side surface of PE base film, and drying to form ceramic coating, wherein the thickness of ceramic coating is 1-2 μm.
Example 2
Preparing a lithium metaaluminate material:
s1, adding 1480g of lithium carbonate with the purity of 99.999 percent and the granularity of 3-15 mu m and 2040g of nano-grade aluminum oxide with the purity of 99.9 percent and the granularity of 20nm into a ball milling tank made of aluminum oxide, adding 500mL of deionized water, ball milling for 3 hours under the conditions that the ball material weight ratio is 1:1.2, the ball distribution ratio is R3:R 5:R10:R20=5:3:1:1 and the ball milling tank rotating speed is 25R/min, after ball milling is finished, drying at 130 ℃ for 35min, heating to 715 ℃ at the heating rate of 5 ℃/min in a sintering furnace, performing heat preservation and sintering for 6h, heating to 830 ℃ at the heating rate of 5 ℃/min, performing heat preservation and sintering for 3.5h, and cooling to room temperature along with the furnace to obtain a sintered material A;
s2, adding deionized water into the hydrogenation tank, and continuously introducing CO from the bottom of the hydrogenation tank 2 The gas is continuously introduced into CO for 15min (the gas flow rate is 7L/min) 2 Slowly adding the material obtained by crushing the sintering material A under the condition of gas, wherein the weight ratio of the material obtained by crushing the sintering material A to deionized water is 1:20, and continuously introducing CO under the stirring condition of 25r/min 2 Reacting the gas for 65min, and stopping introducing CO 2 Standing for 5h, centrifugally separating, washing the obtained precipitate with deionized water for 3 times, drying, and pulverizing to obtain powder B;
and S3, heating the powder B to 930 ℃ in a sintering furnace at a heating rate of 5 ℃/min, preserving heat and sintering for 50min, cooling to room temperature, and then performing jet milling to submicron order.
A ceramic separator was prepared in the same manner as in example 1.
Example 3
Preparing a lithium metaaluminate material:
s1, adding 1480g of lithium carbonate with the purity of 99.999 percent and the granularity of 3-15 mu m and 2040g of nano-grade aluminum oxide with the purity of 99.9 percent and the granularity of 20nm into a ball milling tank made of aluminum oxide, adding 500mL of deionized water, ball milling for 4 hours under the conditions that the ball material weight ratio is 1:1.3, the ball distribution ratio is R3:R 5:R10:R20=5:3:1:1 and the ball milling tank rotating speed is 25R/min, after ball milling is finished, drying at 130 ℃ for 35 minutes, heating to 530 ℃ in a sintering furnace at a heating rate of 5 ℃/min, preserving heat and sintering for 9.5 hours, heating to 730 ℃ at a heating rate of 5 ℃/min, preserving heat and sintering for 4.5 hours, and cooling to room temperature along with a furnace to obtain a sintered material A;
s2, adding deionized water into the hydrogenation tank, and continuously introducing CO from the bottom of the hydrogenation tank 2 The gas is continuously introduced into CO for 15min (the gas flow rate is 8L/min) 2 Slowly adding the material obtained by crushing the sintering material A under the condition of gas, wherein the weight ratio of the material obtained by crushing the sintering material A to deionized water is 1:20, and continuously introducing CO under the stirring condition of 25r/min 2 Reacting the gas for 90min, and stopping introducing CO 2 Standing for 4h, centrifugally separating, washing the obtained precipitate with deionized water for 3 times, drying, and pulverizing to obtain powder B;
and S3, heating the powder B to 930 ℃ in a sintering furnace at a heating rate of 5 ℃/min, preserving heat and sintering for 50min, cooling to room temperature, and then performing jet milling to submicron order.
Comparative example 1
The only differences between comparative example 1 and example 1 are: the sintering conditions in S1 are different, and the specific steps are as follows:
preparing a lithium metaaluminate material:
s1, adding 740g of lithium carbonate with the purity of 99.999 percent and the granularity of 3-15 mu m and 1020g of nano-grade aluminum oxide with the purity of 99.9 percent and the granularity of 20nm into a ball milling tank made of aluminum oxide, ball milling for 2.5 hours under the conditions that the ball weight ratio is 1:1, the ball distribution ratio is R3:R5:R 10:R20=5:3:1:1 and the rotating speed of the ball milling tank is 25R/min, heating to 830 ℃ in a sintering furnace at the heating rate of 5 ℃/min after ball milling is finished, preserving heat and sintering for 3 hours, and cooling to room temperature along with the furnace to obtain a sintering material A;
s2, adding deionized water into the hydrogenation tank, and continuously introducing CO from the bottom of the hydrogenation tank 2 The gas is continuously introduced into CO for 10min (the gas flow rate is 5L/min) 2 Slowly adding under the condition of gasFeeding the material obtained by crushing the sintering material A, wherein the weight ratio of the material obtained by crushing the sintering material A to deionized water is 1:20, and continuously feeding CO under the stirring condition of 25r/min 2 The gas reacts for 45min, and then CO is stopped being introduced 2 Standing for 6h, centrifugally separating, washing the obtained precipitate with deionized water for 3 times, drying, and pulverizing to obtain powder B;
and S3, heating the powder B to 930 ℃ in a sintering furnace at a heating rate of 5 ℃/min, preserving heat, sintering for 60min, cooling to room temperature, and performing jet milling to submicron order.
A ceramic separator was prepared in the same manner as in example 1.
Comparative example 2
Comparative example 2 differs from example 1 only in that: the sintering conditions in S1 are different, and the specific steps are as follows:
preparing a lithium metaaluminate material:
s1, adding 740g of lithium carbonate with the purity of 99.999 percent and the granularity of 3-15 mu m and 1020g of nano-grade aluminum oxide with the purity of 99.9 percent and the granularity of 20nm into a ball milling tank made of aluminum oxide, ball milling for 2.5 hours under the conditions that the ball weight ratio is 1:1, the ball distribution ratio is R3:R5:R 10:R20=5:3:1:1 and the rotating speed of the ball milling tank is 25R/min, heating to 715 ℃ in a sintering furnace at the heating rate of 5 ℃/min after ball milling, preserving heat and sintering for 7.5 hours, and cooling to room temperature along with the furnace to obtain a sintering material A;
s2, adding deionized water into the hydrogenation tank, and continuously introducing CO from the bottom of the hydrogenation tank 2 The gas is continuously introduced into CO for 10min (the gas flow rate is 5L/min) 2 Slowly adding the material obtained by crushing the sintering material A under the condition of gas, wherein the weight ratio of the material obtained by crushing the sintering material A to deionized water is 1:20, and continuously introducing CO under the stirring condition of 25r/min 2 The gas reacts for 45min, and then CO is stopped being introduced 2 Standing for 6h, centrifugally separating, washing the obtained precipitate with deionized water for 3 times, drying, and pulverizing to obtain powder B;
and S3, heating the powder B to 930 ℃ in a sintering furnace at a heating rate of 5 ℃, preserving heat and sintering for 60min, cooling to room temperature, and then performing jet milling to submicron order.
A ceramic separator was prepared in the same manner as in example 1.
Comparative example 3
Comparative example 3 differs from example 1 only in that: s3, not sintering, wherein the specific steps are as follows:
preparing a lithium metaaluminate material:
s1, adding 740g of lithium carbonate with the purity of 99.999 percent and the granularity of 3-15 mu m and 1020g of nano-grade aluminum oxide with the purity of 99.9 percent and the granularity of 20nm into a ball milling tank made of aluminum oxide, ball milling for 2.5 hours under the conditions that the ball weight ratio is 1:1, the ball distribution ratio is R3:R5:R 10:R20=5:3:1:1 and the ball milling tank rotating speed is 25R/min, after ball milling, firstly heating to 715 ℃ in a sintering furnace at the heating rate of 5 ℃/min, preserving heat, sintering for 7.5 hours, then heating to 830 ℃ at the heating rate of 5 ℃/min, preserving heat, sintering for 3 hours, and cooling to room temperature along with the furnace to obtain a sintering material A;
s2, adding deionized water into the hydrogenation tank, and continuously introducing CO from the bottom of the hydrogenation tank 2 The gas is continuously introduced into CO for 10min (the gas flow rate is 5L/min) 2 Slowly adding the material obtained by crushing the sintering material A under the condition of gas, wherein the weight ratio of the material obtained by crushing the sintering material A to deionized water is 1:20, and continuously introducing CO under the stirring condition of 25r/min 2 The gas reacts for 45min, and then CO is stopped being introduced 2 Standing for 6h, centrifugally separating, washing the obtained precipitate with deionized water for 3 times, drying, and pulverizing to obtain powder B;
s3, jet-pulverizing the powder B to submicron order.
A ceramic separator was prepared in the same manner as in example 1.
Comparative example 4
Comparative example 4 differs from example 1 only in that: the hydrogenation treatment is not carried out, and the specific steps are as follows:
preparing a lithium metaaluminate material:
s1, adding 740g of lithium carbonate with the purity of 99.999 percent and the granularity of 3-15 mu m and 1020g of nano-grade aluminum oxide with the purity of 99.9 percent and the granularity of 20nm into a ball milling tank made of aluminum oxide, ball milling for 2.5 hours under the conditions that the ball weight ratio is 1:1, the ball distribution ratio is R3:R5:R 10:R20=5:3:1:1 and the ball milling tank rotating speed is 25R/min, after ball milling, firstly heating to 715 ℃ in a sintering furnace at the heating rate of 5 ℃/min, preserving heat and sintering for 7.5 hours, then heating to 830 ℃ at the heating rate of 5 ℃, preserving heat and sintering for 3 hours, and cooling to room temperature along with the furnace to obtain a sintering material A;
s2, after the sintering material A is crushed, heating to 930 ℃ in a sintering furnace at a heating rate of 5 ℃/min, preserving heat and sintering for 60min, cooling to room temperature, and then carrying out jet milling to submicron order, thus obtaining the material.
A ceramic separator was prepared in the same manner as in example 1.
Test examples
The ceramic separators prepared in examples 1 to 3 and comparative examples 1 to 4 were respectively used to assemble lithium cobaltate, lithium iron phosphate and ternary 622 lithium ion batteries, and electrochemical properties thereof were measured. The testing method comprises the following steps: the above assembled battery was first short-circuited for discharge, the maximum rate was tested, and then the capacity retention rate of the short-circuited battery was tested under the condition of 1C, and the results are shown in table 1:
TABLE 1
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the lithium metaaluminate material is characterized by comprising the following steps of:
s1, mixing lithium carbonate with nano-scale aluminum oxide, uniformly ball-milling, sintering at 530-725 ℃ for 6-9.5 hours, and then sintering at 730-860 ℃ for 2.5-4.5 hours to obtain a sintered material A;
s2, crushing the sintering material A, carrying out hydrogenation treatment, standing for a period of time, carrying out solid-liquid separation, washing the obtained solid substance, and drying and crushing to obtain powder B;
s3, sintering the powder B at 930-965 ℃ for 45-65min to obtain the composite material.
2. The method of preparing a lithium metaaluminate material according to claim 1, wherein the molar ratio of lithium carbonate to nano-sized aluminum oxide is (1-1.05): 1.
3. the method for preparing a lithium metaaluminate material according to claim 1, wherein the granularity of the lithium carbonate is 3-60 μm and the purity is 99.9% -99.999%; the granularity of the nano-scale aluminum oxide is 20-65nm, and the purity is 99-99.9%.
4. The lithium metaaluminate material, the preparation method and the application thereof according to claim 1, wherein in S1, the ball milling is dry ball milling or wet ball milling; the conditions of the dry ball milling are as follows: ball-material ratio is 1:1-1:1.3, ball milling time is 2.5-4h, ball matching ratio is R3:R5:R10:R20=5:3:1:1, and rotating speed is 25-28R/min; the wet ball milling conditions are as follows: ball material ratio is 1:1-1:1.3, ball milling time is 2.5-4h, ball matching ratio is R3:R5:R10:R20=5:3:1:1, rotating speed is 25-28R/min, ball milling solvent is water, and water consumption is 15-30% of the sum of mass of lithium carbonate and aluminum oxide.
5. The method for preparing a lithium metaaluminate material according to claim 1, wherein in S2, the specific step of performing the hydrogenation treatment comprises: deionized water is added into a hydrogenation device, and CO is continuously introduced from the bottom of the hydrogenation device 2 Continuously introducing CO into the gas for 10-15min 2 Slowly adding the materials obtained by crushing the sintering material A under the condition of gas, and continuously introducing CO under the stirring 2 The hydrogenation reaction is carried out for 45-90 min.
6. The method for preparing a lithium metaaluminate material according to claim 1, wherein in S3, after sintering is completed, further comprising: and cooling the material obtained by sintering, and crushing to submicron level.
7. A lithium metaaluminate material prepared by the preparation method according to any one of claims 1 to 8.
8. The use of the lithium metaaluminate material according to claim 7 as a separator coating material for lithium ion batteries.
9. A lithium ion battery separator comprising a base film and a ceramic coating applied to at least one side surface of the base film, the ceramic coating comprising the lithium metaaluminate material of claim 7.
10. The lithium ion battery separator according to claim 9, wherein the mass of the lithium metaaluminate material accounts for 97.5-98% of the mass of the ceramic coating.
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| CN115490251A (en) * | 2022-10-28 | 2022-12-20 | 华能国际电力股份有限公司 | Lithium metaaluminate powder and preparation method and application thereof |
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