CN111477819B - Full-ceramic diaphragm for lithium ion battery and preparation method thereof - Google Patents

Full-ceramic diaphragm for lithium ion battery and preparation method thereof Download PDF

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Publication number
CN111477819B
CN111477819B CN202010332684.0A CN202010332684A CN111477819B CN 111477819 B CN111477819 B CN 111477819B CN 202010332684 A CN202010332684 A CN 202010332684A CN 111477819 B CN111477819 B CN 111477819B
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lithium ion
ion battery
diaphragm
lithium
ceramic diaphragm
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CN111477819A (en
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薛兵
杨阔
李冬妮
李晔
李芳菲
雒锋
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Jilin University
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Jilin University
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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
    • 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
    • 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
    • H01M50/431—Inorganic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a full ceramic diaphragm for a lithium ion battery and a preparation method thereof, belonging to the field of diaphragm materials. The method takes natural porous mineral diatomite as a main raw material, adds lithium carbonate and a small amount of titanium dioxide, uses a small amount of binder, and is subjected to compression molding and high-temperature calcination to obtain the all-ceramic diaphragm for the lithium ion battery, which takes titanium-doped lithium silicate as a main component. The thermal stability temperature of the full-ceramic diaphragm exceeds 800 ℃, the problem that the traditional lithium ion battery is ignited due to the short circuit inside the battery caused by the thermal shrinkage deformation of the diaphragm is effectively avoided, and the safety of the lithium ion battery is remarkably improved. The all-ceramic diaphragm has high porosity and high liquid absorption rate, and the titanium-doped lithium silicate component in the diaphragm can promote the dissociation of lithium salt in the lithium ion battery electrolyte, promote the lithium ion transmission and improve the capacity retention rate of the battery in large-current charging and discharging and long-time operation.

Description

Full-ceramic diaphragm for lithium ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery diaphragms, and relates to a high-temperature-resistant power type lithium ion battery diaphragm suitable for large-current charging and discharging and a preparation method thereof.
Background art:
the wide application of lithium ion batteries has promoted the development of electric vehicles, and separators as core components of batteries are coming to a new round of development. The diaphragm used in the power lithium ion battery is obviously different from the diaphragm of the common lithium ion battery, the diaphragm of the power lithium ion battery provides power for vehicles such as automobiles and the like, and higher voltage, higher power and more electric quantity are required to be provided, so that higher requirements are provided for the diaphragm. At present, commercial lithium ion battery separator materials are mainly porous polyolefin such as Polyethylene (PE), polypropylene/polyethylene (PP/PE) films and the like, and although polyolefin separators have various advantages when used in lithium ion batteries, the polyolefin separators have the problems of low porosity, poor wettability to electrolyte and the like, and are not favorable for large-current charge and discharge and long-time use capacity maintenance of power batteries. Meanwhile, the polyolefin film has the defects of large high-temperature shrinkage rate and low thermal stability, which are main reasons for high-temperature thermal failure of the battery and short circuit and fire in the battery. Therefore, the development of a novel power type lithium ion battery diaphragm product which is resistant to high temperature and suitable for large-current charging and discharging is an urgent task for developing electric vehicles.
Coating modification of polyolefin separator is a conventional means for improving thermal stability, and coating of inorganic ceramic particles is the first choice. Inorganic ceramic particles, such as boehmite, alumina, silica, titania, zirconia, etc., are selected as a coating material of a polyolefin separator due to excellent thermal stability and electrolyte wettability, to improve thermal stability of the polyolefin separator. For example, patent CN201611228378.2 reports that the thermal stability, puncture resistance and tensile strength of the prepared coating type diaphragm are obviously improved by using polyolefin microporous membrane as a matrix and alumina as a coating. On the basis, patent CN201710533227.6 reports a technology of coating ceramic slurry on both sides of a base film, which effectively avoids the problem of high-temperature curling of a coating type diaphragm, so that the battery diaphragm obtains lower shrinkage rate, and the battery safety is improved. With the advance of the technology, composite separators with multilayer structures have appeared in succession, such as lithium ion battery separators reported in patent CN201911140350.7, which are composed of a polymer base material, a heat-resistant composite functional layer composed of a nano-ceramic material and an aramid polymer, and a polyvinylidene fluoride protective layer. In the aspect of ceramic coating technology, electrostatic spinning mode reported by patent CN201911071686.2 and ceramic material physical vapor deposition technology reported by patent CN201510292908.9 appear. In addition, in order to eliminate the restriction of the polymer base film on the thermal stability of the material, patent CN201810688460.6 does not use the polymer material as a coating base film, and directly coats ceramic slurry formed by mixing ceramic particles and an adhesive on the surface of the positive electrode plate, thereby realizing the integration of the positive electrode diaphragm of the lithium ion battery, and further improving the safety of the battery. However, the polymer binder in the ceramic coating also has the defect of easy shrinkage and decomposition at high temperature, which is a negative factor influencing the thermal stability of the diaphragm. Therefore, the development of the diaphragm material made of all ceramic materials is an effective measure for improving the thermal stability of the lithium ion battery.
The invention content is as follows:
the invention aims to eliminate potential safety hazards of a battery caused by poor thermal stability of a lithium ion battery diaphragm and improve the capacity retention rate of the battery in large-current charging and discharging and long-time operation. Therefore, the natural porous mineral diatomite is used as a main raw material, lithium carbonate is mixed, a small amount of titanium dioxide is doped, the mixture is formed by using an organic binder, and the porous ceramic diaphragm taking titanium-doped lithium silicate as a main component is formed after high-temperature calcination.
The purpose of the invention is realized by the following technical scheme:
evenly mixing the diatomite, the lithium carbonate, the titanium dioxide, the binder and the solvent according to a certain mass ratio, carrying out compression molding, and drying at 75 ℃; placing the dried molded sample in a muffle furnace to be calcined to 810-850 ℃, and preserving heat for 7-10 hours; the calcined sample is subjected to surface polishing to obtain the all-ceramic diaphragm for the lithium ion battery; the binder is polyvinylidene fluoride (PVDF); the solvent is N-methylpyrrolidone (NMP) or N, N-Dimethylformamide (DMF); the mass ratio of the diatomite to the lithium carbonate to the titanium dioxide to the binder to the solvent is 40-60: 35-55: 0.2-0.6: 0.4-0.8: 4; and placing the dried molded sample in a muffle furnace for calcining, wherein the heating rate is 3-6 ℃/min.
Has the advantages that: the invention utilizes the porous structure of diatomite and selects the diatomite as a main raw material to prepare the full ceramic diaphragm with the porous structure. The gas generated by the high-temperature decomposition of the lithium carbonate is beneficial to improving the porosity of the ceramic diaphragm, and further is beneficial to the rapid transmission of lithium ions in the large-current charging and discharging process. The titanium-doped lithium silicate generated by the reaction of the lithium carbonate, the titanium dioxide and the silicon dioxide in the diatomite can remarkably promote the dissociation of lithium salt in the lithium ion battery electrolyte, promote the lithium ion transmission and improve the multiplying power and the cycle performance of the battery. The diaphragm obtained by the invention does not contain any organic component, and the inorganic component of the diaphragm is stable at high temperature and is not decomposed, and the preparation temperature is higher, so that the thermal stability temperature of the all-ceramic diaphragm is higher than 800 ℃, and the safety problem of internal short circuit of the battery caused by shrinkage deformation of the traditional lithium ion battery diaphragm due to heating is thoroughly solved. In addition, the all-ceramic diaphragm has high porosity and good electrolyte wettability, so that the mass transfer efficiency of lithium ions in the battery is effectively promoted, and the capacity retention rate of the battery in large-current charging and discharging and long-time operation is improved.
Description of the drawings:
FIG. 1 is a scanning electron microscope photograph of a full ceramic lithium ion battery diaphragm
FIG. 2 shows the rate capability curve of a lithium ion battery using a fully ceramic separator
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples:
diatomite, lithium carbonate, titanium dioxide, polyvinylidene fluoride (PVDF), N-methyl pyrrolidone (NMP) or N, N-Dimethylformamide (DMF) according to a certain mass ratio of 40-60: 35-55: 0.2-0.6: 0.4-0.8: 4, uniformly mixing, carrying out compression molding, and drying at 75 ℃; placing the dried molded sample in a muffle furnace to be calcined to 810-850 ℃, heating up at the rate of 3-6 ℃/min, and keeping the temperature for 7-10 hours; and polishing the surface of the calcined sample to obtain the all-ceramic diaphragm for the lithium ion battery.
Example 1
Diatomite, lithium carbonate, titanium dioxide, polyvinylidene fluoride (PVDF), N-methyl pyrrolidone (NMP) according to a certain mass ratio of 40: 55: 0.2: 0.8: 4, uniformly mixing, carrying out compression molding, and drying at 75 ℃; placing the dried molded sample in a muffle furnace, calcining to 810 ℃, heating at the rate of 6 ℃/min, and keeping the temperature for 10 hours; and polishing the surface of the calcined sample to obtain the all-ceramic diaphragm for the lithium ion battery.
The porosity of the all-ceramic diaphragm for the lithium ion battery is 56.3 percent, the liquid absorption rate is 193 percent, and the discharge specific capacity under the multiplying power of 10C is 91.8mAh g-1(lithium iron phosphate battery system).
Example 2
Diatomite, lithium carbonate, titanium dioxide, polyvinylidene fluoride (PVDF), N-methyl pyrrolidone (NMP) according to a certain mass ratio of 50: 45: 0.4: 0.6: 4, uniformly mixing, carrying out compression molding, and drying at 75 ℃; placing the dried molded sample in a muffle furnace, calcining to 830 ℃, heating at a rate of 5 ℃/min, and keeping the temperature for 9 hours; and polishing the surface of the calcined sample to obtain the all-ceramic diaphragm for the lithium ion battery.
The porosity of the all-ceramic diaphragm for the lithium ion battery is 57.9 percent, the liquid absorption rate is 202 percent, and the discharge specific capacity under the multiplying power of 10 ℃ is 92.1mAh g-1(lithium iron phosphate battery system).
Example 3
Diatomite, lithium carbonate, titanium dioxide, polyvinylidene fluoride (PVDF), N-Dimethylformamide (DMF) according to a certain mass ratio of 55: 40: 0.5: 0.5: 4, uniformly mixing, carrying out compression molding, and drying at 75 ℃; placing the dried molded sample in a muffle furnace, calcining to 840 ℃, heating at a rate of 4 ℃/min, and keeping the temperature for 8 hours; and polishing the surface of the calcined sample to obtain the all-ceramic diaphragm for the lithium ion battery.
The porosity of the all-ceramic diaphragm for the lithium ion battery is 52.4%, the liquid absorption rate is 183%, and the discharge specific capacity under the multiplying power of 10 ℃ is 89.8mAh g-1(lithium iron phosphate battery system).
Example 4
Diatomite, lithium carbonate, titanium dioxide, polyvinylidene fluoride (PVDF), N-Dimethylformamide (DMF) according to a certain mass ratio of 60: 35: 0.6: 0.4: 4, uniformly mixing, carrying out compression molding, and drying at 75 ℃; placing the dried molded sample in a muffle furnace, calcining to 850 ℃, heating at a rate of 3 ℃/min, and keeping the temperature for 7 hours; and polishing the surface of the calcined sample to obtain the all-ceramic diaphragm for the lithium ion battery.
The porosity of the all-ceramic diaphragm for the lithium ion battery is 59.1 percent, the liquid absorption rate is 217 percent, and the discharge specific capacity under the multiplying power of 10 ℃ is 95.8mAh g-1(lithium iron phosphate battery system).

Claims (3)

1. A preparation method of an all-ceramic diaphragm for a lithium ion battery is characterized by comprising the following steps:
evenly mixing the diatomite, the lithium carbonate, the titanium dioxide, the binder and the solvent according to a certain mass ratio, carrying out compression molding, and drying at 75 ℃; placing the dried molded sample in a muffle furnace to be calcined to 810-850 ℃, and preserving heat for 7-10 hours; the calcined sample is subjected to surface polishing to obtain the all-ceramic diaphragm for the lithium ion battery; the binder is polyvinylidene fluoride (PVDF); the solvent is N-methylpyrrolidone (NMP) or N, N-Dimethylformamide (DMF); the mass ratio of the diatomite to the lithium carbonate to the titanium dioxide to the binder to the solvent is 40-60: 35-55: 0.2-0.6: 0.4-0.8: 4.
2. the preparation method of the all-ceramic separator for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: and placing the dried molded sample in a muffle furnace for calcining, wherein the heating rate is 3-6 ℃/min.
3. The utility model provides a lithium ion battery is with full ceramic diaphragm which characterized in that: obtainable by the process according to any one of claims 1-2.
CN202010332684.0A 2020-04-24 2020-04-24 Full-ceramic diaphragm for lithium ion battery and preparation method thereof Active CN111477819B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109285983A (en) * 2018-09-28 2019-01-29 东北大学 Using lithium ion solid electrolyte piece as button lithium battery of diaphragm and preparation method thereof
CN110165294A (en) * 2019-05-31 2019-08-23 浙江国能锂业股份有限公司 A kind of preparation method of highly conductive lithium ion solid electrolyte
CN110931689A (en) * 2019-10-29 2020-03-27 东北大学 Perovskite type lithium ion solid electrolyte diaphragm and preparation and use methods thereof

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KR100659851B1 (en) * 2005-04-27 2006-12-19 삼성에스디아이 주식회사 Lithium secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109285983A (en) * 2018-09-28 2019-01-29 东北大学 Using lithium ion solid electrolyte piece as button lithium battery of diaphragm and preparation method thereof
CN110165294A (en) * 2019-05-31 2019-08-23 浙江国能锂业股份有限公司 A kind of preparation method of highly conductive lithium ion solid electrolyte
CN110931689A (en) * 2019-10-29 2020-03-27 东北大学 Perovskite type lithium ion solid electrolyte diaphragm and preparation and use methods thereof

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