CN119812339A - A composite positive electrode flame retardant additive and its preparation method and application - Google Patents
A composite positive electrode flame retardant additive and its preparation method and application Download PDFInfo
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- CN119812339A CN119812339A CN202510019348.3A CN202510019348A CN119812339A CN 119812339 A CN119812339 A CN 119812339A CN 202510019348 A CN202510019348 A CN 202510019348A CN 119812339 A CN119812339 A CN 119812339A
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Abstract
本发明属于阻燃材料技术领域，公开了一种复合型正极阻燃添加剂及其制备方法和应用。该复合型正极阻燃添加剂，包括固体阻燃剂和包覆固体阻燃剂的导电聚合物层。在固体阻燃剂表面包覆一层导电聚合物，导电聚合物层可改善正极片的导电性能，从而提高正极片的倍率性能，同时阻隔阻燃剂与正极活性材料直接接触，减少阻燃剂对电池电化学性能的不利影响；内核阻燃剂在电池发生热失控初期，吸收大量热量，捕获正极材料释放的活性氧，从而阻止电池发生热失控。The present invention belongs to the technical field of flame retardant materials, and discloses a composite positive electrode flame retardant additive, a preparation method and application thereof. The composite positive electrode flame retardant additive comprises a solid flame retardant and a conductive polymer layer coating the solid flame retardant. A layer of conductive polymer is coated on the surface of the solid flame retardant, and the conductive polymer layer can improve the conductivity of the positive electrode sheet, thereby improving the rate performance of the positive electrode sheet, while blocking the direct contact between the flame retardant and the positive electrode active material, reducing the adverse effects of the flame retardant on the electrochemical performance of the battery; the core flame retardant absorbs a large amount of heat in the early stage of thermal runaway of the battery, captures the active oxygen released by the positive electrode material, and thus prevents the battery from thermal runaway.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a composite anode flame-retardant additive, and a preparation method and application thereof.
Background
The lithium ion battery has been widely used in the fields of portable electronic products, electric automobiles, aerospace and energy storage systems due to the advantages of high energy density, good cycling stability, environmental protection, wide working temperature range and the like. However, the lithium ion battery has serious limitation in commercialization progress due to thermal runaway safety problems caused by overcharge, short circuit, impact, and the like.
Currently, methods for improving the safety of lithium ion batteries include modification of electrolyte, surface treatment of separator, modification of cathode, development of battery management system, and application of flame retardant. The application of the flame retardant is one of the simplest and effective methods, and alkyl phosphate esters such as trimethyl phosphate, triethyl phosphate and tributyl phosphate are widely studied in recent years, are early flame retardants of lithium ion batteries, have good flame retardant effects, but have poor compatibility with electrode materials due to high viscosity, reduce the ionic conductivity of electrolyte and shorten the cycle life of the batteries. When the flame retardant is directly added to the battery, an adverse effect of the flame retardant on the electrochemical performance of the battery is unavoidable. In a power battery, a ternary material and lithium iron phosphate are mainly used, the electronic conductivity is low, the multiplying power performance is poor, and in the high-multiplying power charge and discharge process, the surface of a positive electrode material is easy to release more active oxygen due to rapid migration of lithium ions, so that the thermal runaway of the battery is induced.
Therefore, there is a need to develop a flame retardant additive that improves the rate capability of the positive electrode material while achieving a flame retardant effect.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a composite anode flame retardant additive, and a preparation method and application thereof. The composite anode flame retardant additive has flame retardant effect and electronic conductivity, can reduce adverse effect of the flame retardant on electrochemical performance of the battery while ensuring the safety performance of the battery, and further improves the multiplying power performance of the battery when being applied to the lithium ion battery.
The first aspect of the invention provides a composite positive electrode flame retardant additive.
Specifically, the composite anode flame retardant additive comprises a solid flame retardant and a conductive polymer layer coating the solid flame retardant.
Preferably, the conductive polymer layer accounts for 2-15% of the total weight of the composite positive electrode flame retardant additive, and more preferably 3-12%.
Preferably, the solid flame retardant accounts for 85-98% of the total weight of the composite positive electrode flame retardant additive, and more preferably 88-97%.
Preferably, the solid flame retardant comprises at least one of ammonium polyphosphate (APP), melamine polyphosphate (MPP), calcium hypophosphite, aluminum hypophosphite, antimony trioxide, magnesium hydroxide, aluminum hydroxide.
Preferably, the particle size of the solid flame retardant is 0.5 to 12. Mu.m, more preferably 1 to 10. Mu.m.
Preferably, the composition of the conductive polymer layer includes at least one of polypyrrole, polyaniline, or polythiophene.
Preferably, the polypyrrole has a structural general formula:
wherein R 1、R2 is independently selected from H, -COOH, -COOCH 3、-CmH2m+1 saturated alkyl, 1<m is less than or equal to 6;
R 3 is selected from H, -CH 3、-CH＝CH2、-CH2CH2OOCC(CH3)＝CH2 (ethyl methacrylate);
10≤n≤800。
Preferably, the polyaniline has a structural general formula:
Wherein R 4 is selected from H or-CH 3;
R 5 is selected from H, -CH 3、-CH2CH3、-Cl、-OCH3;
10≤n≤800。
preferably, the polythiophene has a structural general formula:
R 6、R7 is selected from H, -COOH, -COOCH 3、-B(OH)2、-CmH2m+1 saturated alkyl, 1<m is less than or equal to 6;
10≤n≤800。
the second aspect of the invention provides a preparation method of the composite anode flame retardant additive.
Specifically, the preparation method of the composite anode flame retardant additive comprises the following steps:
(1) Mixing a solid flame retardant with a solvent to obtain a suspension A;
(2) And mixing an oxidant with the acid solution to obtain a solution B, adding the monomer and the solution B into the suspension A, and mixing and reacting to obtain the composite anode flame retardant additive.
Preferably, in the step (1), the solvent is at least one selected from toluene, dichloromethane, tetrahydrofuran, acetonitrile, N-dimethylformamide and N-methylpyrrolidone.
Preferably, in step (1), the mixing is performed by ultrasonic dispersion.
Preferably, in the step (2), the oxidant is at least one of ammonium persulfate ((NH 4)2S2O8), potassium dichromate (K 2Cr2O7), ferric trichloride (FeCl 3), and hydrogen peroxide (H 2O2).
Preferably, in the step (2), the acid solution comprises at least one of hydrochloric acid, beta-naphthalene sulfonic acid, dodecylbenzene sulfonic acid and camphorsulfonic acid. The acid solution may be aqueous solution of hydrochloric acid, beta-naphthalene sulfonic acid, dodecylbenzene sulfonic acid or camphorsulfonic acid. The acid liquor has the function of doping the modified conductive polymer to improve the conductivity of the conductive polymer, and the intrinsic state of the conductive polymer such as polypyrrole, polyaniline, polythiophene and the like is non-conductive.
Preferably, in step (2), the monomer is selected from at least one of pyrrole, aniline, thiophene and derivatives thereof.
Preferably, in step (2), the molar ratio of the oxidizing agent to the monomer is (0.3-1.2): 1, more preferably (0.5-1): 1.
Preferably, in step (2), the mass of the monomer is 0.5 to 5.5% of the mass of the flame retardant, and more preferably 1 to 5%.
Preferably, in the step (2), the reaction is carried out in an ice-water bath environment for 4-8 hours, and more preferably, the reaction is carried out for 12-24 hours.
Preferably, in the step (2), after the reaction is finished, the method further comprises the processes of suction filtration, washing and drying.
The third aspect of the invention provides the use of a composite positive electrode flame retardant additive.
A battery comprises a positive plate, a diaphragm, electrolyte and a negative plate, wherein the positive plate comprises a positive active material and the composite positive flame retardant additive.
Preferably, the positive electrode active material is selected from at least one of LiCoO 2、LiFePO4 and NCM (nickel cobalt manganese material), and more preferably NCM811.
Preferably, in the positive plate, the mass ratio of the positive electrode active material to the composite positive electrode flame retardant additive is less than 92:5. I.e., the composite positive electrode flame retardant additive needs to be added in a sufficient amount.
Preferably, the negative electrode sheet contains a negative electrode active material, and the negative electrode active material is at least one selected from graphite, silicon carbon, silicon oxygen, pure silicon and lithium titanate, and more preferably graphite.
Compared with the prior art, the invention has the following beneficial effects:
The invention provides a composite anode flame retardant additive, which comprises a core solid flame retardant and a conductive polymer coating layer. The conductive polymer coated on the surface of the solid flame retardant has good electron conduction capability, not only can improve the conductive performance of the positive plate and further improve the multiplying power performance of the positive electrode, but also can prevent the flame retardant from directly contacting with the positive electrode active material, and reduce the adverse effect of the flame retardant on the electrochemical performance of the battery.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1
A composite positive electrode flame retardant additive comprises a solid flame retardant and a conductive polymer layer coating the solid flame retardant. The composition of the conductive polymer layer includes polypyrrole.
The preparation method of the composite anode flame retardant additive comprises the following steps:
(1) Adding 10g of solid flame retardant (ammonium polyphosphate) into N-methylpyrrolidone (NMP) organic solvent for ultrasonic dispersion for 30min to obtain suspension A;
(2) And (2) dissolving 0.43g of ammonium persulfate in 1M (M represents mol/L) dodecylbenzene sulfonic acid solution to obtain solution B, adding 0.25g of pyrrole monomer and the solution B into the suspension A in the step (1), uniformly mixing, reacting for 6 hours in an ice water bath environment, and carrying out suction filtration, washing and drying after the reaction is finished to finally obtain the composite anode flame retardant additive.
A preparation process of a soft package battery comprises the following steps:
(1) Adding NCM811 (LiNi 0.8Co0.1Mn0.1O2) positive electrode active material, the composite positive electrode flame retardant additive prepared in the embodiment, SP carbon black conductive agent and PVDF polyvinylidene fluoride binder into NMP solvent according to the mass ratio of 92:5:1.5:1.5, fully and uniformly mixing to obtain positive electrode slurry, controlling the solid content to be 70%, uniformly coating the positive electrode slurry on aluminum foil, and baking, rolling, slitting and die cutting to obtain a positive electrode plate;
(2) Adding graphite anode material, SP carbon black conductive agent, SBR styrene-butadiene rubber and CMC sodium carboxymethyl cellulose into water according to the mass ratio of 96:1.5:1:1.5, fully and uniformly mixing to obtain anode slurry, controlling the solid content to be 50%, uniformly coating the anode slurry on copper foil, and baking, rolling, slitting and die-cutting to obtain the anode sheet.
(3) The diaphragm is a commercial alumina ceramic diaphragm, the volume ratio of electrolyte to electrolyte of 1M LiPF 6/EC (ethylene carbonate) +DEC (diethyl carbonate) +DMC (dimethyl carbonate) is 1:1:1, and the positive plate, the electrolyte, the diaphragm and the negative plate are laminated to form the soft package battery.
Example 2
The preparation method of the composite anode flame retardant additive comprises the following steps:
(1) Adding 10g of solid flame retardant (ammonium polyphosphate) into N-methylpyrrolidone (NMP) organic solvent for ultrasonic dispersion for 30min to obtain suspension A;
(2) And (3) dissolving 0.17g of ammonium persulfate in 1M (M represents mol/L) dodecylbenzene sulfonic acid solution to obtain solution B, adding 0.1g of pyrrole monomer and the solution B into the suspension A in the step (1), uniformly mixing, reacting for 6 hours in an ice water bath environment, and carrying out suction filtration, washing and drying after the reaction is finished to finally obtain the composite anode flame retardant additive.
The preparation process of the soft pack battery was the same as in example 1.
Example 3
The preparation method of the composite anode flame retardant additive comprises the following steps:
(1) Adding 10g of solid flame retardant (ammonium polyphosphate) into N-methylpyrrolidone (NMP) organic solvent for ultrasonic dispersion for 30min to obtain suspension A;
(2) And (3) dissolving 0.85g of ammonium persulfate in 1M (M represents mol/L) dodecylbenzene sulfonic acid solution to obtain solution B, adding 0.5g of pyrrole monomer and the solution B into the suspension A in the step (1), uniformly mixing, reacting for 6 hours in an ice water bath environment, and carrying out suction filtration, washing and drying after the reaction is finished to finally obtain the composite anode flame retardant additive.
The preparation process of the soft pack battery was the same as in example 1.
Example 4
Compared with example 1, the difference of example 4 is that the composite positive electrode flame retardant additive, the SP carbon black conductive agent and the PVDF polyvinylidene fluoride binder are added into NMP solvent according to the mass ratio of 87:10:1.5:1.5, and are fully and uniformly mixed to prepare positive electrode slurry, and the rest processes are exactly the same as those of example 1.
Comparative example 1
Comparative example 1 differs from example 1 only in that the same amount of ammonium polyphosphate was used instead of the composite positive flame retardant additive of example 1 to prepare a soft pack battery, as compared with example 1. That is, in comparative example 1, the ammonium polyphosphate was not subjected to the coating treatment.
Comparative example 2
Comparative example 2 differs from example 1 only in that a composite positive electrode flame retardant additive was not used in the process of preparing a pouch battery, as compared with example 1.
Comparative example 3
Comparative example 2 differs from example 1 only in that the pyrrole of example 1 was replaced with an equivalent amount of polyureaformaldehyde during the preparation of the composite positive electrode flame retardant additive, and the remainder of the procedure was identical to that of example 1.
Comparative example 4
Compared with example 1, the comparative example 4 only differs in that the composite positive electrode flame retardant additive, the SP carbon black conductive agent and the PVDF polyvinylidene fluoride binder are added into NMP solvent according to the mass ratio of 96:1:1.5:1.5, and are fully and uniformly mixed to prepare positive electrode slurry, and the rest processes are exactly the same as those of example 1.
Product effect test
The soft package batteries prepared in the above examples and comparative examples were subjected to first coulombic efficiency, rate performance and needling experiments, and the test methods are as follows, and the test results are shown in table 1:
First coulombic efficiency, namely, performing charge and discharge test on the soft package battery at 0.1C multiplying power, wherein the voltage working range is 2.75-4.2V, and the first coulombic efficiency is=first discharge capacity/first charge capacity multiplied by 100%;
the rate performance is that the rate discharge performance of the soft package battery at 0.1C, 0.5C, 1C and 2C is tested at room temperature;
The needling experiment is that a high temperature resistant steel needle (needle point angle 60 DEG, surface of the needle is smooth and clean, no rust, oxide layer and greasy dirt) is used in a state of 100% SOC (full charge), the needle penetrates from the direction perpendicular to the cell at a speed of (25+/-5) mm/s, the needle stays in the cell, and the cell is observed for 1h to monitor whether fire explosion occurs.
TABLE 1
As can be seen from table 1, the composite positive flame retardant additive prepared by the embodiment of the invention is applied to a battery, and not only the safety of the battery is remarkably improved, but also the electrochemical performance of the battery is remarkably improved.
Claims (10)
1. A composite positive electrode flame retardant additive, comprising a solid flame retardant and a conductive polymer layer coating the solid flame retardant.
2. The composite positive electrode flame retardant additive of claim 1, wherein the conductive polymer layer comprises 2-15% of the total weight of the composite positive electrode flame retardant additive.
3. The composite positive electrode flame retardant additive of claim 1, wherein the solid flame retardant comprises 85-98% of the total weight of the composite positive electrode flame retardant additive.
4. The composite positive electrode flame retardant additive of claim 1, wherein the solid flame retardant comprises at least one of ammonium polyphosphate, melamine polyphosphate, calcium hypophosphite, aluminum hypophosphite, antimony trioxide, magnesium hydroxide, aluminum hydroxide.
5. The composite anode flame retardant additive of claim 1, wherein the composition of the conductive polymer layer comprises at least one of polypyrrole, polyaniline, or polythiophene.
6. The composite anode flame retardant additive of claim 5, wherein the polypyrrole has a structural formula:
wherein R 1、R2 is independently selected from H, -COOH, -COOCH 3、-CmH2m+1 saturated alkyl, 1<m is less than or equal to 6;
R 3 is selected from H, -CH 3、-CH＝CH2、-CH2CH2OOCC(CH3)＝CH2 (ethyl methacrylate);
10≤n≤800;
And/or, the polyaniline has a structural general formula:
Wherein R 4 is selected from H or-CH 3;
R 5 is selected from H, -CH 3、-CH2CH3、-Cl、-OCH3;
10≤n≤800;
and/or, the polythiophene has a structural general formula:
R 6、R7 is selected from H, -COOH, -COOCH 3、-B(OH)2、-CmH2m+1 saturated alkyl, 1<m is less than or equal to 6;
10≤n≤800。
7. The method for preparing the composite anode flame retardant additive according to any one of claims 1 to 6, comprising the steps of:
(1) Mixing a solid flame retardant with a solvent to obtain a suspension A;
(2) And mixing an oxidant with the acid solution to obtain a solution B, adding the monomer and the solution B into the suspension A, and mixing and reacting to obtain the composite anode flame retardant additive.
8. The method according to claim 7, wherein the oxidizing agent is at least one of ammonium persulfate, potassium dichromate, ferric trichloride, and hydrogen peroxide, and/or the acid solution comprises at least one of hydrochloric acid, beta-naphthalene sulfonic acid, dodecylbenzene sulfonic acid, and camphorsulfonic acid, and/or the monomer is at least one selected from pyrrole, aniline, thiophene, and derivatives thereof.
9. The process according to claim 7, wherein the molar ratio of the oxidizing agent to the monomer is (0.3-1.2): 1, and/or the mass of the monomer is 0.5-5.5% of the mass of the flame retardant, and/or the reaction is carried out in an ice water bath environment for 4-8 hours.
10. A battery comprising a positive electrode sheet, a separator, an electrolyte, and a negative electrode sheet, the positive electrode sheet comprising a positive electrode active material and the composite positive electrode flame retardant additive of any one of claims 1-6.
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Citations (5)
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|---|---|---|---|---|
| WO2011080306A2 (en) * | 2009-12-31 | 2011-07-07 | Chemische Fabrik Budenheim Kg | Flame retardant composition for thermoplastic molding compounds |
| CN111883826A (en) * | 2020-09-09 | 2020-11-03 | 蜂巢能源科技有限公司 | Electrolyte material and preparation method and application thereof |
| CN115911390A (en) * | 2022-12-26 | 2023-04-04 | 蜂巢能源科技(上饶)有限公司 | Electrode plate, preparation method thereof and battery |
| CN117013080A (en) * | 2023-09-06 | 2023-11-07 | 四川鸿鹏新材料有限公司 | Flame-retardant microcapsule, preparation method thereof and flame-retardant electrolyte |
| CN117976908A (en) * | 2024-02-05 | 2024-05-03 | 吉林大学 | Flame-retardant composite material and preparation method and application thereof |
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- 2025-01-07 CN CN202510019348.3A patent/CN119812339A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011080306A2 (en) * | 2009-12-31 | 2011-07-07 | Chemische Fabrik Budenheim Kg | Flame retardant composition for thermoplastic molding compounds |
| CN111883826A (en) * | 2020-09-09 | 2020-11-03 | 蜂巢能源科技有限公司 | Electrolyte material and preparation method and application thereof |
| CN115911390A (en) * | 2022-12-26 | 2023-04-04 | 蜂巢能源科技(上饶)有限公司 | Electrode plate, preparation method thereof and battery |
| CN117013080A (en) * | 2023-09-06 | 2023-11-07 | 四川鸿鹏新材料有限公司 | Flame-retardant microcapsule, preparation method thereof and flame-retardant electrolyte |
| CN117976908A (en) * | 2024-02-05 | 2024-05-03 | 吉林大学 | Flame-retardant composite material and preparation method and application thereof |
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