CN105048022A - Novel coating material for lithium ion battery and preparation method thereof - Google Patents
Novel coating material for lithium ion battery and preparation method thereof Download PDFInfo
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- CN105048022A CN105048022A CN201510354400.7A CN201510354400A CN105048022A CN 105048022 A CN105048022 A CN 105048022A CN 201510354400 A CN201510354400 A CN 201510354400A CN 105048022 A CN105048022 A CN 105048022A
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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
- H01M10/058—Construction or manufacture
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention belongs to the technical field of lithium ion batteries, in particular relates to a novel coating material for a lithium ion battery and a preparation method thereof. The coating material is a microcapsule with a core-shell structure, an inner core is made of a phase change heat accumulation material, and an outer shell is made of an inorganic oxide. The preparation method of the coating is implemented by using a micro-emulsion polymerization method. Compared with the traditional coating material applied to the lithium ion battery, the coating material disclosed by the invention has the advantages that intelligent heat control performance is achieved, the safety performance can be improved by the outer shell of the coating layer, heat can be absorbed through phase change by the inner core on a condition of thermal runway occurred in the battery, moreover, latent heat of the phase change is high, and thus the function of intelligent heat control is achieved.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery coating material and preparation method thereof with intelligence control hot property.
Background technology
Since the lithium ion battery commercialization nineties in 20th century, due to its have that voltage is high, the advantage such as energy density is large, have extended cycle life, memory-less effect, be widely used in consumption electronic product, also be applied to as electrokinetic cell at present in all kinds of pure electronic, hybrid vehicle, its safety problem also highlights day by day.
In general, lithium ion battery comprises positive/negative plate, be clipped in barrier film between the two, electrolyte and seal casinghousing, the characteristic of its septation blocks electronics exactly, passes through ion, its Main Function forms ion transfer passage, make the both positive and negative polarity of battery separate, prevent its short circuit, therefore the quality of membrane properties directly affects the excellence of battery performance simultaneously.
At present, commercial diaphragm for lithium ion battery is generally PP or PE material, and the security performance of microcellular structure to battery of barrier film is most important.When battery is when overcharging or temperature is too high, barrier film meeting closed pore, form open circuit at inside battery, prevent the continuation of temperature from raising, fusing refers to that barrier film melts completely, shrinks so that battery explosion.Its closed pore of the barrier film of different substrate materials and fusing-off temperature difference, the closed pore temperature of PP barrier film is higher, and fusing-off temperature is also higher; The closed pore temperature of PE barrier film is lower, and fusing-off temperature is also lower.And for lithium ion battery, for meeting the requirement of its security performance, need the barrier film that closed pore temperature is low and fusing-off temperature is high, the safety problems such as the battery explosion that just can prevent it from occurring that thermal runaway causes in abnormal cases is on fire.
In order to improve the thermostability of polyalkene diaphragm to strengthen the fail safe of lithium ion battery, the main scheme adopted applies at the single or double of polyolefin film the porous active layer be made up of inorganic particle and binding agent at present, forms the composite diaphragm of organic and inorganic.Because inorganic particulate has higher mechanical strength and thermal stability, the security performance of battery can be improved to a certain extent.But, if battery is when overcharging or internal short-circuit occurs, electric current or temperature raise instantaneously and cause battery to occur thermal runaway, and inorganic coating does not possess the function of release heat, heat is put aside instantaneously and cannot be discharged fast, and battery still may occur that blast causes security incident.
Summary of the invention
The object of the invention is to: a kind of new type lithium ion battery coating material and the preparation method with the function of intelligent heat release are provided, can be coated on lithium ion battery separator or both positive and negative polarity pole piece, battery can be made to realize the release of heat in the moment that temperature raises suddenly thus avoid the safety problem of battery.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of new type lithium ion battery coating material, is characterized in that: described coating material is the microcapsules with nucleocapsid structure, and core group becomes phase-change heat-storage material, and shell consists of inorganic oxide.
Preferably, described phase-change heat-storage material is inorganic or one or more in organic phase change material, and its phase transition temperature is between 50 DEG C ~ 300 DEG C.
Preferably, described shell is one or more in alundum (Al2O3), silicon dioxide, zirconium dioxide, TiO 2 particles.
Preferably, the particle diameter of described coating material is between 5 ~ 100nm.
Preferably, described coating material can be coated on lithium ion battery separator or lithium ion both positive and negative polarity pole piece, and its coating thickness is at 2 ~ 20 μm.
Preferably, the preparation method of described new type lithium ion battery coating material, concrete preparation method is as follows:
(1) microemulsion of coating material is prepared: first the kernel component of coating material and phase-change heat-storage material are carried out melting, after add the acid solution of surfactant, both fully carry out mix and blend, form milky emulsion, then add cosurfactant and form microemulsion, microemulsion being stirred the regular hour makes it stablize;
(2) preparation of the microcapsules of nucleocapsid structure: the precursor adding shell inorganic material in above-mentioned microemulsion, stirred after a period of time, and what realize kernel is coated, thus realizes the preparation of the microcapsules of nucleocapsid structure.
Preferably, the surfactant in step (1) is the one in dodecyl sodium sulfate, lauryl sodium sulfate.
Preferably, the cosurfactant in step (1) is the one in positive n-amyl alcohol, n-butanol.
Beneficial effect of the present invention is:
(1) coating material of the present invention has intelligence control hot property, the shell of coat can improve security performance, and kernel when thermal runaway appears in battery, can realize the absorption to heat by phase transformation, and latent heat of phase change is large, thus play the effect of intelligence control heat.Namely the moment that coating material of the present invention can raise suddenly at battery temperature realizes the release of heat, thus solve single inorganic oxide aluminized coating can not the problem of release heat.
(2) coating material of the present invention, can be coated on anode pole piece or cathode pole piece, like this when thermal runaway appears in battery, also can realize the abrupt release of heat and improve the security performance of battery.
(3) coating material structure of the present invention is nucleocapsid structure, and the inorganic oxide particle of its shell, by coated for the phase-change heat-storage material of kernel, there will not be phase-change material to undergo phase transition near transformation temperature to absorb heat and the fluid leakage problems that causes.
(4) ratio of coating material of the present invention actual temp in the preparation, mixing time and core-shell structure copolymer material, can change for the endothermic temperature in lithium ion battery and caloric receptivity according to coating material, thus meet the needs of lithium ion battery for safe thermal release.
Accompanying drawing explanation
Fig. 1 is the structural representation of coating material of the present invention;
Fig. 2 is wherein a kind of DSC curve of coating material of the present invention;
Fig. 3 is the coating schematic diagram of coating material of the present invention;
Reference numeral: 1-coating material kernel; 2-coating material surfactant; 3-coating material shell; 4-coating material; 5-coated substrates.
Embodiment
In conjunction with Figure of description 1-3 and the following examples 1-3, the present invention is further described:
Example 1:
In the round-bottomed flask of 50ml, add the stearic acid of 1.0g, the dodecyl sodium sulfate of 0.5g is dissolved in the aqueous solution of nitric acid of 20ml, join in round-bottomed flask, 80 DEG C are heated under oil bath, the emulsion of white is formed under stirring condition, add the n-amyl alcohol of 0.8ml, continue to stir the microemulsion that about 30min forms clear, the tetraethyl orthosilicate of 0.5ml is dropwise added under the condition stirred, stir the regular hour, then the ammoniacal liquor adding 0.2ml continues to stir, stop after the reaction regular hour stirring, ageing a period of time carries out centrifuge washing, three times are washed with water and ethanol, drying i.e. obtained sample.
Example 2:
In the round-bottomed flask of 50ml, add the palmitic acid of 1.0g, the lauryl sodium sulfate of 0.5g is dissolved in the aqueous hydrochloric acid solution of 20ml, join in round-bottomed flask, 70 DEG C are heated under oil bath, the emulsion of white is formed under stirring condition, add the n-amyl alcohol of 0.8ml, continue to stir the microemulsion that about 30min forms clear, the Alumina gel of 0.5ml is dropwise added under the condition stirred, stir the regular hour, then the ammoniacal liquor adding 0.2ml continues to stir, stop after the reaction regular hour stirring, ageing a period of time carries out centrifuge washing, three times are washed with water and ethanol, drying i.e. obtained sample.
Example 3:
In the round-bottomed flask of 50ml, add the paraffin of 1.0g, the dodecyl sodium sulfate of 0.5g is dissolved in the aqueous solution of nitric acid of 20ml, join in round-bottomed flask, 90 DEG C are heated under oil bath, the emulsion of white is formed under stirring condition, add the n-butanol of 0.8ml, continue to stir the microemulsion that about 30min forms clear, the butyl titanate of 0.5ml is dropwise added under the condition stirred, stir the regular hour, then the ammoniacal liquor adding 0.2ml continues to stir, stop after the reaction regular hour stirring, ageing a period of time carries out centrifuge washing, three times are washed with water and ethanol, drying i.e. obtained sample.
Claims (8)
1. a new type lithium ion battery coating material, is characterized in that: described coating material is the microcapsules with nucleocapsid structure, and core group becomes phase-change heat-storage material, and shell consists of inorganic oxide.
2. new type lithium ion battery coating material according to claim 1, is characterized in that: described phase-change heat-storage material is inorganic or one or more in organic phase change material, and its phase transition temperature is between 50 DEG C ~ 300 DEG C.
3. new type lithium ion battery coating material according to claim 1, is characterized in that: described shell is one or more in alundum (Al2O3), silicon dioxide, zirconium dioxide, TiO 2 particles.
4. new type lithium ion battery coating material according to claim 1, is characterized in that: the particle diameter of described coating material is between 5 ~ 100nm.
5. new type lithium ion battery coating material according to claim 1, is characterized in that: described coating material can be coated on lithium ion battery separator or lithium ion both positive and negative polarity pole piece, and its coating thickness is at 2 ~ 20 μm.
6. the preparation method of the new type lithium ion battery coating material according to claim 1-5 any one, is characterised in that: concrete preparation method is as follows:
(1) microemulsion of coating material is prepared: first the kernel component of coating material and phase-change heat-storage material are carried out melting, after add the acid solution of surfactant, both fully carry out mix and blend, form milky emulsion, then add cosurfactant and form microemulsion, microemulsion being stirred the regular hour makes it stablize;
(2) preparation of the microcapsules of nucleocapsid structure: the precursor adding shell inorganic material in above-mentioned microemulsion, stirred after a period of time, and what realize kernel is coated, thus realizes the preparation of the microcapsules of nucleocapsid structure.
7. the preparation method of new type lithium ion battery coating material according to claim 6, is characterised in that: the surfactant in step (1) is the one in dodecyl sodium sulfate, lauryl sodium sulfate.
8. the preparation method of new type lithium ion battery coating material according to claim 6, is characterised in that: the cosurfactant in step (1) is the one in positive n-amyl alcohol, n-butanol.
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Cited By (5)
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| CN105932200A (en) * | 2016-05-26 | 2016-09-07 | 北京新能源汽车股份有限公司 | Lithium-ion battery composite membrane and preparation method thereof and lithium-ion battery |
| CN109554167A (en) * | 2019-01-03 | 2019-04-02 | 北京科技大学 | A kind of nanocapsules and preparation method thereof |
| CN110165166A (en) * | 2019-05-13 | 2019-08-23 | 北京石油化工学院 | A kind of method of microemulsion assisted in situ coated lithium ion battery positive electrode |
| CN111916632A (en) * | 2020-07-24 | 2020-11-10 | 清华大学 | Composite particle for battery, battery separator, and lithium ion battery |
| WO2023061083A1 (en) * | 2021-10-12 | 2023-04-20 | 宁德时代新能源科技股份有限公司 | Phase-change microcapsule, separator, electrode plate, battery, and electrical device |
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| CN110165166A (en) * | 2019-05-13 | 2019-08-23 | 北京石油化工学院 | A kind of method of microemulsion assisted in situ coated lithium ion battery positive electrode |
| CN111916632A (en) * | 2020-07-24 | 2020-11-10 | 清华大学 | Composite particle for battery, battery separator, and lithium ion battery |
| WO2023061083A1 (en) * | 2021-10-12 | 2023-04-20 | 宁德时代新能源科技股份有限公司 | Phase-change microcapsule, separator, electrode plate, battery, and electrical device |
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Address after: 230000 Yaohai Industrial Zone, Hefei New District, Anhui, No. D weft Road, No. 7 Applicant after: Hefei Guoxuan High-Tech Power Energy Co., Ltd. Address before: 230000 Yaohai Industrial Zone, Hefei New District, Anhui, No. D weft Road, No. 7 Applicant before: Hefei Guoxuan High-Tech Power Energy Co., Ltd. |
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Application publication date: 20151111 |