CN110993860A - Preparation method of lithium battery diaphragm additive and lithium battery diaphragm - Google Patents
Preparation method of lithium battery diaphragm additive and lithium battery diaphragm Download PDFInfo
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- CN110993860A CN110993860A CN201911398487.2A CN201911398487A CN110993860A CN 110993860 A CN110993860 A CN 110993860A CN 201911398487 A CN201911398487 A CN 201911398487A CN 110993860 A CN110993860 A CN 110993860A
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- Prior art keywords
- lithium battery
- additive
- battery diaphragm
- stirring
- montmorillonite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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 provides a preparation method of a lithium battery diaphragm additive and a lithium battery diaphragm, which comprises the following steps of a, reacting ammonium polyphosphate with chlorine-containing organic matters at the temperature of 90-125 ℃ for 8-20 hours, adding hydrochloric acid into the solution after the reaction is finished, continuously stirring for 1-3 hours to obtain ammonium polyphosphate chloride, b, mixing the ammonium polyphosphate chloride with montmorillonite in the step a, fully stirring to obtain organic modified nano-montmorillonite, c, mixing β nucleating agent, antioxidant and the organic modified nano-montmorillonite in the step b, and stirring to obtain the lithium battery diaphragm additive.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a lithium battery diaphragm additive and a lithium battery diaphragm.
Background
The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, an electrolyte and a diaphragm. The preparation method of the lithium ion battery diaphragm mainly comprises two main methods of melt stretching (MSCS) and Thermally Induced Phase Separation (TIPS). The lithium ion battery diaphragm is a main component of the lithium ion battery, the quality of the performance of the diaphragm determines the interface structure of the battery and the internal resistance of the battery, and further influences the capacity, the cycle performance, the charge-discharge current density and other key characteristics of the battery, so that the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery.
In the prior art, a lithium ion battery with high energy density can generate a large amount of heat when the battery is overcharged due to large current carried by the lithium ion battery, and the battery is easy to cause combustion and explosion due to thermal runaway. Meanwhile, the sharp lithium dendrite diaphragm is mainly made of polyolefin materials, so that the sharp lithium dendrite diaphragm is poor in heat shrinkage resistance and easy to shrink or melt when heated, large cavities are generated, and the anode and the cathode are in contact with each other to cause short circuit. In addition, lithium ions are easy to generate relatively sharp lithium dendrites on the surfaces of the positive and negative electrodes in the repeated migration process, and the sharp lithium dendrites are easy to pierce a thin diaphragm to cause short circuit.
In order to solve the above problems, it is currently common practice to coat an inorganic material coating on the surface of the separator to improve the thermal stability and other physical properties of the separator. However, the ceramic coating and the polyolefin microporous diaphragm of the base material cannot form an organic whole, the bonding interface strength is weak, the coating is easy to fall off in the later period, the safety of the lithium ion battery diaphragm is not improved, and the performance of the lithium ion battery is influenced due to the fallen ceramic nano powder.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a preparation method of a lithium battery diaphragm additive and a lithium battery diaphragm, which solve the problems of poor thermal stability and short circuit caused by contact between a positive electrode and a negative electrode due to easy shrinkage or melting when being heated of the traditional lithium battery diaphragm, and also solve the problem of short circuit caused by piercing of a thinner diaphragm by sharp lithium dendrites generated on the surfaces of the positive electrode and the negative electrode of the traditional lithium battery diaphragm.
The preparation method of the lithium battery diaphragm additive is characterized by comprising the following steps:
a. preparing an intercalation ion exchanger: reacting the ammonium polyphosphate with a chlorine-containing organic matter at the temperature of 90-125 ℃ for 8-20 h, adding hydrochloric acid into the solution after the reaction is finished, and continuously stirring for 1-3 h to obtain chlorinated ammonium polyphosphate;
b. preparing organic modified nano montmorillonite: mixing the chlorinated ammonium polyphosphate salt in the step a with montmorillonite, and fully stirring to obtain the organic modified nano montmorillonite;
c. and c, preparing the lithium battery diaphragm additive, namely mixing and stirring β nucleating agent, antioxidant and the organic modified nano montmorillonite in the step b to obtain the lithium battery diaphragm additive.
Further, the stirring conditions of the step b are as follows: under the ultrasonic oscillation condition of 500W-1000W, uniformly mixing and stirring at the speed of 1200-2000 r/min for 0.5 h-2 h.
Further, the stirring conditions of the step c are as follows: mixing and stirring uniformly at a speed of 3000-6000 r/min for 10-15 min.
Furthermore, in the step c, 1-99 parts of β crystal form nucleating agent, 5-95 parts of antioxidant and 1-99 parts of organic modified nano montmorillonite agent are mixed according to the mass part ratio.
Furthermore, according to the mass portion ratio, 5-95 portions of the β crystal form nucleating agent, 10-90 portions of the antioxidant and 5-95 portions of the organic modified nano-montmorillonite agent are preferred.
Further, the β crystal form nucleating agent is preferably a carboxylate nucleating agent, and the antioxidant is preferably an oil-soluble antioxidant.
Further, the chlorine-containing organic matter is preferably chloroalkane.
The lithium battery diaphragm is obtained after the additive prepared by the preparation method of the lithium battery diaphragm and polypropylene are subjected to high-temperature blending, extrusion, stretching and shaping.
The preparation method of the lithium battery diaphragm additive and the lithium battery diaphragm have the beneficial effects that:
1. the production process has simple procedures, does not need to coat an inorganic material coating on the surface of the diaphragm, and is easy to popularize and apply in actual production.
2. The prepared lithium battery diaphragm has excellent thermal stability and puncture resistance.
3. The prepared lithium battery diaphragm has higher safety performance.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the table in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The table, which is incorporated in and constitutes a part of the specification, illustrates embodiments of the invention and, together with the description, serves to explain the principles of the invention. In these tables, like table designations are used to indicate like elements. The tables in the following description are some, but not all embodiments of the invention. For those skilled in the art, other tables can be obtained from these tables without creative efforts.
For further understanding of the present invention, the lithium battery separator additive provided by the present invention is described below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1:
preparing an intercalation ion exchanger, dissolving ammonium polyphosphate in water, heating to 50-80 ℃, taking 60 ℃, adding dichloroethane, reacting at 90 ℃ for 8 hours, adding hydrochloric acid into the solution, continuously stirring and reacting for 1 hour, distilling, drying and crushing to obtain chlorinated ammonium polyphosphate.
Preparing modified nano montmorillonite, selecting 100g of montmorillonite of 200 meshes, fully dissolving in water to form montmorillonite suspension, heating to 60-80 ℃, and taking 60 ℃. Slowly adding the chlorinated ammonium polyphosphate salt serving as the intercalation ion exchanger, uniformly mixing, stirring at the power of 500W under the ultrasonic oscillation condition for 0.5 hour at the stirring speed of 1200r/min, and performing suction filtration, drying and grinding after stirring to obtain the organic nano montmorillonite.
Preparing a lithium battery diaphragm additive, mixing 5 parts of antioxidant BHA, 5 parts of modified organic nano montmorillonite and 90 parts of β nucleating agent lithium benzoate according to the mass part ratio, stirring at a stirring speed of 3000r/min until the mixture is uniform, and stirring for 10 minutes to obtain the lithium battery diaphragm additive.
The prepared lithium battery diaphragm additive is blended with polypropylene at high temperature, extruded, stretched and shaped to obtain the lithium battery diaphragm.
Example 2:
preparing an intercalation ion exchanger, dissolving ammonium polyphosphate in water, heating to 50-80 ℃, taking 50 ℃, adding dichloroethane, reacting at 100 ℃ for 10 hours, adding hydrochloric acid into the solution, continuously stirring and reacting for 2 hours, distilling, drying and crushing to obtain chlorinated ammonium polyphosphate.
Preparing modified nano montmorillonite, selecting 100g of montmorillonite of 200 meshes, fully dissolving in water to form montmorillonite suspension, heating to 60-80 ℃, and taking 70 ℃. Slowly adding the chlorinated ammonium polyphosphate salt serving as the intercalation ion exchanger, uniformly mixing, stirring at the stirring speed of 1500r/min for 2.0h under the condition of 800W power ultrasonic oscillation, and performing suction filtration, drying and grinding after stirring to obtain the organic nano montmorillonite.
Preparing a lithium battery diaphragm additive, mixing 5 parts of antioxidant BHA, 5 parts of modified organic nano montmorillonite and 90 parts of β parts of nucleating agent lithium benzoate according to the mass part ratio, stirring at the stirring speed of 4500r/min until the mixture is uniform, and stirring for 12 minutes to obtain the lithium battery diaphragm additive.
The prepared lithium battery diaphragm additive is blended with polypropylene at high temperature, extruded, stretched and shaped to obtain the lithium battery diaphragm.
Example 3:
preparing an intercalation ion exchanger, dissolving ammonium polyphosphate in water, heating to 50-80 ℃, taking 80 ℃, adding dichloroethane, reacting for 20 hours at the temperature of 125 ℃, continuously adding hydrochloric acid into the solution, stirring and reacting for 3 hours, distilling, drying and crushing to obtain chlorinated ammonium polyphosphate.
Preparing modified nano montmorillonite, selecting 100g of montmorillonite of 200 meshes, fully dissolving in water to form montmorillonite suspension, heating to 60-80 ℃, and taking 80 ℃. Slowly adding the intercalation ion exchanger chlorinated ammonium polyphosphate salt, uniformly mixing, stirring at a stirring speed of 2000r/min for 1.0h under the condition of 1000W power ultrasonic oscillation, and performing suction filtration, drying and grinding after stirring to obtain the organic nano montmorillonite.
Preparing a lithium battery diaphragm additive, mixing 5 parts of antioxidant BHA, 5 parts of modified organic nano montmorillonite and 90 parts of β parts of lithium benzoate serving as a nucleating agent according to the mass part ratio, stirring at a stirring speed of 6000r/min until the mixture is uniform, and stirring for 15 minutes to obtain the lithium battery diaphragm additive.
The prepared lithium battery diaphragm additive is blended with polypropylene at high temperature, extruded, stretched and shaped to obtain the lithium battery diaphragm.
Comparative example 1
The comparative example 1 is a lithium battery diaphragm obtained by blending and extruding a traditional β crystal form nucleating agent, an antioxidant and a reinforcing agent with polypropylene at a high temperature, stretching and shaping.
Table 1 shows the performance test results of the lithium battery separator at 120 ℃:
as can be seen from table 1, the separator prepared by using the lithium battery separator additive of the present invention has excellent thermal stability. The diaphragm with the thickness of 20 mu m has larger thermal shrinkage at the temperature of more than 120 ℃ in the traditional diaphragm with the thickness of 20 mu m, the puncture strength of the diaphragm is 3.0-4.0N, while the diaphragm provided by the invention has smaller thermal shrinkage at the temperature of 120 ℃, the puncture strength can reach 5.0-6.0N, and the lithium battery diaphragm additive greatly improves the use safety of the lithium battery diaphragm.
Table 2 shows the results of performance tests on the lithium battery separators of comparative example 1 and example 1
The lithium battery separators of comparative example 1 and example 1 were subjected to a closed cell temperature test and a rupture temperature test, respectively. Before heating and temperature rising, the pressure of gas passing through the diaphragm at a constant speed is respectively kept at 0.1MPa, 0.2MPa and 0.5MPa, and the average value is obtained after repeated sampling and determination for three times, wherein the specific test data is shown in Table 2:
table 2 results of performance tests of lithium battery separators of comparative example 1 and example 1 for a plurality of times
In the above embodiment: the percentage ratios used, not specifically noted, are mass (weight) percentage ratios (wt% is mass percentage); the proportions used, not specifically noted, are mass (weight) proportions; the parts by weight may all be kilograms or tons.
In the above embodiment: the process parameters (temperature, time, concentration, etc.) and the amounts of the components in each step are within the range, and any point can be applicable.
The above-described aspects may be implemented individually or in various combinations, and such variations are within the scope of the present invention.
In this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such article or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of additional like elements in the article or device comprising the element.
The above embodiments are merely to illustrate the technical solutions of the present invention and not to limit the present invention, and the present invention has been described in detail with reference to the preferred embodiments. It will be understood by those skilled in the art that various modifications and equivalent arrangements may be made without departing from the spirit and scope of the present invention and it should be understood that the present invention is to be covered by the appended claims.
Claims (8)
1. The preparation method of the lithium battery diaphragm additive is characterized by comprising the following steps:
a. preparing an intercalation ion exchanger: reacting the ammonium polyphosphate with a chlorine-containing organic matter at the temperature of 90-125 ℃ for 8-20 h, adding hydrochloric acid into the solution after the reaction is finished, and continuously stirring for 1-3 h to obtain chlorinated ammonium polyphosphate;
b. preparing organic modified nano montmorillonite: mixing the chlorinated ammonium polyphosphate salt in the step a with montmorillonite, and fully stirring to obtain the organic modified nano montmorillonite;
c. and c, preparing the lithium battery diaphragm additive, namely mixing and stirring β nucleating agent, antioxidant and the organic modified nano montmorillonite in the step b to obtain the lithium battery diaphragm additive.
2. The method for preparing the lithium battery separator additive according to claim 1, wherein the stirring conditions in the step b are as follows: under the ultrasonic oscillation condition of 500W-1000W, uniformly mixing and stirring at the speed of 1200-2000 r/min for 0.5 h-2 h.
3. The method for preparing the lithium battery separator additive according to claim 1, wherein the stirring conditions in the step c are as follows: mixing and stirring uniformly at a speed of 3000-6000 r/min for 10-15 min.
4. The preparation method of the lithium battery diaphragm additive as claimed in claim 1, wherein in the step c, 1 to 99 parts of the β crystal-form nucleating agent, 5 to 95 parts of the antioxidant and 1 to 99 parts of the organic modified nano-montmorillonite agent are mixed according to the mass part ratio.
5. The preparation method of the lithium battery diaphragm additive as claimed in claim 4, wherein the β crystal form nucleating agent is preferably 5-95 parts, the antioxidant is preferably 10-90 parts, and the organic modified nano-montmorillonite is preferably 5-95 parts by mass.
6. The preparation method of the lithium battery diaphragm additive as claimed in claim 1, wherein the β crystal form nucleating agent is preferably a carboxylate nucleating agent, and the antioxidant is preferably an oil-soluble antioxidant.
7. The method for preparing the lithium battery separator additive according to claim 1, wherein the chlorine-containing organic substance is preferably chloroalkane.
8. A lithium battery separator characterized by: the lithium battery diaphragm is obtained by blending, extruding, stretching and shaping the additive prepared by the preparation method of any one of claims 1 to 7 and polypropylene at high temperature.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911398487.2A CN110993860A (en) | 2019-12-30 | 2019-12-30 | Preparation method of lithium battery diaphragm additive and lithium battery diaphragm |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911398487.2A CN110993860A (en) | 2019-12-30 | 2019-12-30 | Preparation method of lithium battery diaphragm additive and lithium battery diaphragm |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112687880A (en) * | 2020-12-28 | 2021-04-20 | 山东大学 | Lithium-rich material, and modification method and application thereof |
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| CN101724414A (en) * | 2009-12-30 | 2010-06-09 | 江西固康新材料有限公司 | Nano fire-retarding additive and preparation method thereof |
| CN102148346A (en) * | 2011-03-11 | 2011-08-10 | 河南义腾新能源科技有限公司 | Polyolefin microporous diaphragm and preparation method thereof |
| CN102649850A (en) * | 2012-05-14 | 2012-08-29 | 中国乐凯胶片集团公司 | Polyolefin microporous membrane and preparation method thereof |
| CN108346764A (en) * | 2017-12-12 | 2018-07-31 | 北方华锦化学工业股份有限公司 | A kind of preparation method of dry method biaxial tension lithium battery diaphragm |
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2019
- 2019-12-30 CN CN201911398487.2A patent/CN110993860A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724414A (en) * | 2009-12-30 | 2010-06-09 | 江西固康新材料有限公司 | Nano fire-retarding additive and preparation method thereof |
| CN102148346A (en) * | 2011-03-11 | 2011-08-10 | 河南义腾新能源科技有限公司 | Polyolefin microporous diaphragm and preparation method thereof |
| CN102649850A (en) * | 2012-05-14 | 2012-08-29 | 中国乐凯胶片集团公司 | Polyolefin microporous membrane and preparation method thereof |
| CN108346764A (en) * | 2017-12-12 | 2018-07-31 | 北方华锦化学工业股份有限公司 | A kind of preparation method of dry method biaxial tension lithium battery diaphragm |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112687880A (en) * | 2020-12-28 | 2021-04-20 | 山东大学 | Lithium-rich material, and modification method and application thereof |
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