CN115842132B - Lithium battery composite binder and preparation method thereof - Google Patents
Lithium battery composite binder and preparation method thereof Download PDFInfo
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- CN115842132B CN115842132B CN202211712654.8A CN202211712654A CN115842132B CN 115842132 B CN115842132 B CN 115842132B CN 202211712654 A CN202211712654 A CN 202211712654A CN 115842132 B CN115842132 B CN 115842132B
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Abstract
The invention provides a lithium battery composite binder and a preparation method thereof, wherein the lithium battery composite binder comprises a mixture formed by mixing a first polymer emulsion and a second polymer emulsion in any proportion; the first polymer is a polymer formed by copolymerizing a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer capable of undergoing a free radical polymerization reaction with the monomers; the second polymer is a polymer formed by copolymerizing unsaturated carboxylic acid alkyl ester, second alkenyl aromatic monomer, acrylonitrile, vinyl beta-cyclodextrin quaternary ammonium salt, second aliphatic conjugated diene monomer and second other monomers capable of carrying out free radical polymerization reaction with the monomers. The lithium battery composite binder electrolyte disclosed by the invention has the advantages of good tolerance, good binding property, high efficiency and long cycle life.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium battery composite binder and a preparation method thereof.
Background
With the wide development and rapid application of various portable electronic devices and electric vehicles, there is an increasing demand for high-performance lithium batteries, particularly lithium ion batteries, having high capacity, long life, high power and safety. The performance of an electrode, which is one of the key elements of a lithium battery, directly determines the battery efficiency and cycle life. The binder is used as an important preparation raw material of the electrode, and plays a role in ensuring good contact between the active material and the conductive agent, between the active material and the current collector and between the active material and the active material in the electrode, and ensuring that the whole electrode keeps structural stability in the charge-discharge cycle process, thereby ensuring good electronic passage and stable electrical performance in the battery use process. It is seen that it is particularly important to develop a binder for lithium batteries having excellent comprehensive properties and performance stability.
Currently commonly used lithium ion battery binders include styrene-butadiene rubber (SBR), acrylonitrile multipolymers (LA series polymers), and polyvinylidene fluoride (PVDF) types. The poor affinity of SBR and polar electrolyte results in difficult conduction of lithium ions in the binder in the charge and discharge process, increased internal resistance of the battery, and difficulty in meeting the requirement of lithium batteries, especially power batteries, on high-rate charge and discharge. The LA series polymer has over high glass transition temperature, and the pole piece is easy to become hard and brittle, so that the processing performance is poor. For example, they are prone to cracking during coating and streaking after rolling, which have limited their use in lithium batteries, especially power batteries. Although the traditional PVDF (molecular weight is about 100 ten thousand) has better electrochemical stability and excellent flexibility, the traditional PVDF is easy to swell when being acted with propylene carbonate in electrolyte, so that the electrode structure is deformed, and meanwhile, the binding force is reduced, so that the cycle performance of a battery is deteriorated.
In order to solve the problems, chinese patent No. 106602073B discloses a lithium battery composite binder and application thereof, wherein the lithium battery composite binder consists of a flexible binder polytetrafluoroethylene and a rigid binder; the rigid binder is at least one of polyacrylate, acrylonitrile multipolymer, carboxymethyl cellulose and sodium carboxymethyl cellulose; the mass ratio of the two is (6-16) to (1-4). The invention adopts the combination of the flexible adhesive PTFE and the rigid adhesive, and utilizes the characteristic of complementation of the two adhesive properties, thereby slowing down the trend of the decline of the pulse capacity of the lithium-manganese dioxide battery at the end of discharge; meanwhile, organic functional groups such as polyacrylate, acrylonitrile multipolymer, natural cellulose modified substance and the like can coordinate with Mn atoms, so that the reaction sites on the surface of the manganese dioxide of the anode can be reduced, the occurrence of side reactions catalyzed by the manganese dioxide is reduced, the stability of the inside of a lithium-manganese dioxide battery system is improved, and the storage life of a lithium-manganese dioxide battery is prolonged. However, the composite binder electrolyte resistance and compatibility of both binders are to be further improved; the efficiency and cycle life of the lithium battery using the binder are still further improved. Therefore, a more effective method is needed to prepare the lithium battery composite adhesive with good electrolyte tolerance, good adhesive property, high efficiency and long cycle life.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a lithium battery composite binder with good electrolyte tolerance, good bonding performance, high efficiency and long cycle life for a lithium battery using the lithium battery composite binder and a preparation method thereof.
The invention can be realized by the following technical scheme:
the lithium battery composite binder comprises a mixture formed by mixing a first polymer emulsion and a second polymer emulsion in any proportion; the first polymer is a polymer formed by copolymerizing a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer capable of undergoing a free radical polymerization reaction with the monomers; the second polymer is a polymer formed by copolymerizing unsaturated carboxylic acid alkyl ester, second alkenyl aromatic monomer, acrylonitrile, vinyl beta-cyclodextrin quaternary ammonium salt, second aliphatic conjugated diene monomer and second other monomers capable of carrying out free radical polymerization reaction with the monomers;
preferably, the first other monomer is a mixture formed by mixing N-vinylcarbazole, 3- (1, 1-difluoroallyl) quinoxalin-2-ol and tetrahydrofurfuryl methacrylate according to the mass ratio of 1 (1-2): 1.
Preferably, the second other monomer is a mixture formed by mixing 2-acrylamide-2-methylpropanesulfonic acid, 4-propylene oxy-2-hydroxybenzophenone and 2- (1-propylene-2-yl) benzo [ D ] oxazole according to the mass ratio of 1 (1-2): 3.
Preferably, the mass ratio of the first aliphatic conjugated diene monomer, the first alkenyl aromatic monomer, the ethylenically unsaturated carboxylic acid monomer and the first other monomer of the first polymer is (15-35): (40-60): (3-10): (5-10).
Preferably, the first aliphatic conjugated diene monomer is at least one of 2-methyl-1, 3-butadiene, and 2, 3-dimethyl-1, 3-butadiene.
Preferably, the first alkenyl aromatic monomer is at least one of vinyl benzene, vinyl toluene, styrene and alpha-methyl styrene.
Preferably, the ethylenically unsaturated carboxylic acid monomer is at least one of acrylic acid, methacrylic acid and itaconic acid.
Preferably, the mass ratio of the unsaturated carboxylic acid alkyl ester serving as a preparation monomer of the second polymer to the unsaturated carboxylic acid alkyl ester serving as a preparation monomer of the second polymer, the second alkenyl aromatic monomer, acrylonitrile, vinyl beta-cyclodextrin quaternary ammonium salt, the second aliphatic conjugated diene monomer and the second other monomer is (10-30): (15-25): (3-5): (1-4): (3-5): (5-12).
Preferably, the unsaturated carboxylic acid-containing alkyl ester is at least one of ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate and dimethyl itaconate.
Preferably, the second aromatic monomer is at least one of styrene and alpha-methyl styrene.
Preferably, the second aliphatic conjugated diene monomer is at least one of 2-methyl-1, 3-butadiene, and 2, 3-dimethyl-1, 3-butadiene.
Preferably, the solid content of the first polymer emulsion is 15-65wt%, the glass transition temperature is-30-85 ℃, and the granularity is 50-1000nm.
Preferably, the solid content of the second polymer emulsion is 23-65wt%, the glass transition temperature is-35-88 ℃, and the granularity is 50-1000nm.
Preferably, the preparation method of the first polymer emulsion comprises the following steps: uniformly mixing first polymer preparation monomers except the first aliphatic conjugated diene monomer to obtain a first polymer preparation monomer mixture, adding 20-30% of the first polymer preparation monomer mixture into a reaction kettle, introducing 20% of the first aliphatic conjugated diene monomer, water and a first emulsifier into the reaction kettle, mixing and emulsifying, preparing a first polymer seed adhesive by emulsion copolymerization in the presence of 50% of a first initiator by weight, simultaneously dropwise adding the rest of the first polymer preparation monomer mixture, the rest of the first aliphatic conjugated diene monomer and the rest of the initiator, and continuously preserving heat and stirring for 3-5 hours after the completion of the dripping to prepare a first polymer emulsion finished product.
Preferably, the first emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl ether sulfate, ammonium dodecyl ether sulfate and sodium dodecyl benzene sulfonate.
Preferably, the first initiator is at least one of potassium persulfate, sodium persulfate and ammonium persulfate.
Preferably, the mass ratio of the first polymer preparation monomer mixture, the first emulsifier and the first initiator is 100 (2-8): 1-2.
Preferably, the reaction temperature of the emulsion copolymerization is 60-85 ℃ and the reaction time is 3-7h.
Preferably, the preparation method of the second polymer emulsion comprises the following steps: uniformly mixing second polymer preparation monomers except for second aliphatic conjugated diene monomers to obtain a second polymer preparation monomer mixture, adding 20% by weight of the second polymer preparation monomer mixture into a reaction kettle, introducing 20% by weight of the second aliphatic conjugated diene monomers, water and a second emulsifier into the reaction kettle, mixing and emulsifying, and preparing second polymer seed glue by emulsion copolymerization in the presence of 50% by weight of a second initiator; then adding the rest second polymer dropwise to prepare a monomer mixture, the rest second aliphatic conjugated diene monomer and an initiator, after 2 hours, continuing to keep the temperature and stir for 3 hours to prepare a second polymer emulsion finished product.
Preferably, the second emulsifier is one or more of sodium dodecyl ether sulfate, ammonium dodecyl ether sulfate and sodium dodecyl benzene sulfonate.
Preferably, the second initiator is at least one of potassium persulfate, sodium persulfate and ammonium persulfate.
Preferably, the mass ratio of the second polymer preparation monomer mixture, the second emulsifier and the second initiator is 100 (1-8): 1-3.
Preferably, the reaction temperature of the emulsion copolymerization is 50-90 ℃ and the reaction time is 5-9h.
The invention also provides a preparation method of the lithium battery composite binder, which comprises the following steps: and mixing the first polymer emulsion and the second polymer emulsion in proportion, and uniformly stirring to obtain the lithium battery composite adhesive.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the lithium battery composite binder disclosed by the invention can be realized by adopting conventional equipment, has the advantages of low investment, convenient and feasible operation, low energy consumption, high preparation efficiency and high finished product qualification rate, and is suitable for continuous large-scale production. The invention discloses a lithium battery composite binder, wherein the first other monomer is a mixture formed by mixing N-vinyl carbazole, 3- (1, 1-difluoroallyl) quinoxaline-2-alcohol and tetrahydrofurfuryl methacrylate according to the mass ratio of 1 (1-2): 1; the second other monomer is a mixture formed by mixing 2-acrylamide-2-methylpropanesulfonic acid, 4-propylene oxygen-2-hydroxybenzophenone and 2- (1-propylene-2-yl) benzo [ D ] oxazole according to the mass ratio of 1 (1-2): 3. Through reasonable selection of monomers, the prepared polymers have good compatibility, and the introduced monomers can be subjected to multiple effects of electronic effect, steric effect and conjugation effect to prepare the adhesive electrolyte with good tolerance, good adhesive property, high efficiency and long cycle life.
Detailed Description
In order to better understand the technical solution of the present invention, the following describes the product of the present invention in further detail with reference to examples.
The vinyl beta-cyclodextrin quaternary ammonium salt in each embodiment of the invention is reactive beta-cyclodextrin quaternary ammonium salt and is prepared according to the method of the embodiment 6 in ZL201610596491. X.
Example 1
A lithium battery composite binder comprises a mixture formed by mixing a first polymer emulsion and a second polymer emulsion in any proportion; the first polymer is a polymer formed by copolymerizing a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer capable of undergoing a free radical polymerization reaction with the monomers; the second polymer is a polymer formed by copolymerizing unsaturated carboxylic acid alkyl ester, second alkenyl aromatic monomer, acrylonitrile, vinyl beta-cyclodextrin quaternary ammonium salt, second aliphatic conjugated diene monomer and second other monomers capable of carrying out free radical polymerization reaction with the monomers;
the first other monomer is a mixture formed by mixing N-vinylcarbazole, 3- (1, 1-difluoroallyl) quinoxalin-2-ol and tetrahydrofurfuryl methacrylate according to a mass ratio of 1:1:1; the second other monomer is a mixture formed by mixing 2-acrylamide-2-methylpropanesulfonic acid, 4-propylene oxygen-2-hydroxybenzophenone and 2- (1-propylene-2-yl) benzo [ D ] oxazole according to a mass ratio of 1:1:3.
The mass ratio of the first aliphatic conjugated diene monomer to the first alkenyl aromatic monomer to the ethylenically unsaturated carboxylic acid monomer to the first other monomers in the preparation of the first polymer is 15:40:3:5; the first aliphatic conjugated diene monomer is 2-methyl-1, 3-butadiene; the first alkenyl aromatic monomer is vinyl benzene; the ethylenically unsaturated carboxylic acid monomer is acrylic acid.
The mass ratio of the unsaturated carboxylic acid alkyl ester, the second alkenyl aromatic monomer, the acrylonitrile, the vinyl beta-cyclodextrin quaternary ammonium salt, the second aliphatic conjugated diene monomer and the second other monomer of the second polymer is 10:15:3:1:3:5; the unsaturated carboxylic acid alkyl ester is ethyl acrylate; the second alkenyl aromatic monomer is 2-methyl-1, 3-butadiene; the second alkenyl aromatic monomer is styrene; the second aliphatic conjugated diene monomer is 2-methyl-1, 3-butadiene.
The preparation method of the first polymer emulsion comprises the following steps: uniformly mixing first polymer preparation monomers except for first aliphatic conjugated diene monomers to obtain a first polymer preparation monomer mixture, adding 20-30% of the weight of the first polymer preparation monomer mixture into a reaction kettle, introducing 20% of first aliphatic conjugated diene monomers, water and a first emulsifier into the reaction kettle, mixing and emulsifying, preparing a first polymer seed adhesive by emulsion copolymerization in the presence of 50% of a first initiator by weight, simultaneously dropwise adding the rest of the first polymer preparation monomer mixture, the rest of the first aliphatic conjugated diene monomers and the rest of the initiator, and continuously preserving heat and stirring for 3 hours after the completion of the dripping to prepare a first polymer emulsion finished product; the first emulsifier is sodium dodecyl sulfate; the first initiator is potassium persulfate; the mass ratio of the first polymer preparation monomer mixture to the first emulsifier to the first initiator is 100:2:1; the reaction temperature of the emulsion copolymerization is 60 ℃, and the reaction time is 3 hours.
The preparation method of the second polymer emulsion comprises the following steps: uniformly mixing second polymer preparation monomers except for second aliphatic conjugated diene monomers to obtain a second polymer preparation monomer mixture, adding 20% by weight of the second polymer preparation monomer mixture into a reaction kettle, introducing 20% by weight of the second aliphatic conjugated diene monomers, water and a second emulsifier into the reaction kettle, mixing and emulsifying, and preparing second polymer seed glue by emulsion copolymerization in the presence of 50% by weight of a second initiator; then adding the rest second polymer dropwise to prepare a monomer mixture, the rest second aliphatic conjugated diene monomer and an initiator, after 2 hours, continuing to keep the temperature and stir for reaction for 3 hours to prepare a second polymer emulsion finished product; the second emulsifier is sodium dodecyl ether sulfate; the second initiator is potassium persulfate; the mass ratio of the second polymer preparation monomer mixture to the second emulsifier to the second initiator is 100:1:1; the reaction temperature of the emulsion copolymerization is 50 ℃ and the reaction time is 5h.
The preparation method of the lithium battery composite binder comprises the following steps: and mixing the first polymer emulsion and the second polymer emulsion in proportion, and uniformly stirring to obtain the lithium battery composite adhesive Si-Carxyl GD1331.
Example 2
A lithium battery composite binder comprises a mixture formed by mixing a first polymer emulsion and a second polymer emulsion in any proportion; the first polymer is a polymer formed by copolymerizing a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer capable of undergoing a free radical polymerization reaction with the monomers; the second polymer is a polymer formed by copolymerizing unsaturated carboxylic acid alkyl ester, second alkenyl aromatic monomer, acrylonitrile, vinyl beta-cyclodextrin quaternary ammonium salt, second aliphatic conjugated diene monomer and second other monomers capable of carrying out free radical polymerization reaction with the monomers;
the first other monomer is a mixture formed by mixing N-vinylcarbazole, 3- (1, 1-difluoroallyl) quinoxaline-2-alcohol and tetrahydrofurfuryl methacrylate according to a mass ratio of 1:1.2:1; the second other monomer is a mixture formed by mixing 2-acrylamide-2-methylpropanesulfonic acid, 4-propylene oxygen-2-hydroxybenzophenone and 2- (1-propylene-2-yl) benzo [ D ] oxazole according to a mass ratio of 1:1.3:3.
Preparation monomers of the first polymer comprise a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer in a mass ratio of 20:45:5:7; the first aliphatic conjugated diene monomer is 1, 3-butadiene; the first alkenyl aromatic monomer is vinyl toluene; the ethylenically unsaturated carboxylic acid monomer is methacrylic acid.
The mass ratio of the unsaturated carboxylic acid alkyl ester, the second alkenyl aromatic monomer, the acrylonitrile, the vinyl beta-cyclodextrin quaternary ammonium salt, the second aliphatic conjugated diene monomer and the second other monomer of the second polymer is 15:17:3.5:2:3.5:7; the unsaturated carboxylic acid alkyl ester is methyl methacrylate; the second alkenyl aromatic monomer is 1, 3-butadiene; the second alkenyl aromatic monomer is alpha-methyl styrene; the second aliphatic conjugated diene monomer is 1, 3-butadiene.
The preparation method of the first polymer emulsion comprises the following steps: uniformly mixing first polymer preparation monomers except for first aliphatic conjugated diene monomers to obtain a first polymer preparation monomer mixture, adding 23% of the weight of the first polymer preparation monomer mixture into a reaction kettle, introducing 20% of first aliphatic conjugated diene monomers, water and a first emulsifier into the reaction kettle, mixing and emulsifying, preparing a first polymer seed adhesive by emulsion copolymerization in the presence of 50% of a first initiator by weight, simultaneously dropwise adding the rest of the first polymer preparation monomer mixture, the rest of the first aliphatic conjugated diene monomers and the rest of the initiator, and continuously preserving heat and stirring for 3.5 hours after the completion of the dripping to prepare a first polymer emulsion finished product; the first emulsifier is sodium dodecyl ether sulfate; the first initiator is sodium persulfate; the mass ratio of the first polymer preparation monomer mixture, the first emulsifier and the first initiator is 100:4:1.3; the reaction temperature of the emulsion copolymerization is 65 ℃ and the reaction time is 4 hours.
The preparation method of the second polymer emulsion comprises the following steps: uniformly mixing the second polymer preparation monomer to obtain a second polymer preparation monomer mixture, adding 20% of the weight of the second polymer preparation monomer mixture into a reaction kettle, adding water and a second emulsifier into the reaction kettle, mixing and emulsifying, and preparing second polymer seed glue by emulsion copolymerization in the presence of 50% of a second initiator in parts by weight; then adding the rest second polymer dropwise to prepare a monomer mixture and an initiator, after 2 hours of dripping, continuing to perform heat preservation and stirring reaction for 3 hours to prepare a second polymer emulsion finished product; the second emulsifier is dodecyl ether ammonium sulfate; the second initiator is sodium persulfate; the mass ratio of the second polymer preparation monomer mixture to the second emulsifier to the second initiator is 100:3:1.5; the reaction temperature of the emulsion copolymerization is 60 ℃ and the reaction time is 6h.
The preparation method of the lithium battery composite binder comprises the following steps: and mixing the first polymer emulsion and the second polymer emulsion according to a proportion, and uniformly stirring to obtain the lithium battery composite adhesive Si-Carxyl 1332G.
Example 3
A lithium battery composite binder comprises a mixture formed by mixing a first polymer emulsion and a second polymer emulsion in any proportion; the first polymer is a polymer formed by copolymerizing a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer capable of undergoing a free radical polymerization reaction with the monomers; the second polymer is a polymer formed by copolymerizing unsaturated carboxylic acid alkyl ester, second alkenyl aromatic monomer, acrylonitrile, vinyl beta-cyclodextrin quaternary ammonium salt, second aliphatic conjugated diene monomer and second other monomers capable of carrying out free radical polymerization reaction with the monomers;
the first other monomer is a mixture formed by mixing N-vinylcarbazole, 3- (1, 1-difluoroallyl) quinoxaline-2-alcohol and tetrahydrofurfuryl methacrylate according to a mass ratio of 1:1.5:1; the second other monomer is a mixture formed by mixing 2-acrylamide-2-methylpropanesulfonic acid, 4-propylene oxygen-2-hydroxybenzophenone and 2- (1-propylene-2-yl) benzo [ D ] oxazole according to a mass ratio of 1:1.5:3.
Preparation monomers of the first polymer comprise a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer in a mass ratio of 25:50:6:7; the first aliphatic conjugated diene monomer is 2, 3-dimethyl-1, 3-butadiene; the first alkenyl aromatic monomer is styrene; the ethylenically unsaturated carboxylic acid monomer is methacrylic acid.
The mass ratio of the unsaturated carboxylic acid alkyl ester, the second alkenyl aromatic monomer, the acrylonitrile, the vinyl beta-cyclodextrin quaternary ammonium salt, the second aliphatic conjugated diene monomer and the second other monomer of the second polymer is 20:20:4:2.5:4:9; the unsaturated carboxylic acid alkyl ester is ethyl methacrylate; the second alkenyl aromatic monomer is 2, 3-dimethyl-1, 3-butadiene; the second alkenyl aromatic monomer is styrene; the second aliphatic conjugated diene monomer is 2, 3-dimethyl-1, 3-butadiene.
The preparation method of the first polymer emulsion comprises the following steps: uniformly mixing first polymer preparation monomers except for first aliphatic conjugated diene monomers to obtain a first polymer preparation monomer mixture, adding 25% of the weight of the first polymer preparation monomer mixture into a reaction kettle, introducing 20% of first aliphatic conjugated diene monomers, water and a first emulsifier into the reaction kettle, mixing and emulsifying, preparing a first polymer seed adhesive by emulsion copolymerization in the presence of 50% of a first initiator by weight, simultaneously dropwise adding the rest of the first polymer preparation monomer mixture, the rest of the first aliphatic conjugated diene monomers and the rest of the initiator, and continuously preserving heat and stirring for reaction for 4 hours after 2 hours to prepare a first polymer emulsion finished product; the first emulsifier is dodecyl ether ammonium sulfate; the first initiator is ammonium persulfate; the mass ratio of the first polymer preparation monomer mixture to the first emulsifier to the first initiator is 100:6:1.5; the reaction temperature of the emulsion copolymerization is 72 ℃ and the reaction time is 5h.
The preparation method of the second polymer emulsion comprises the following steps: uniformly mixing second polymer preparation monomers except for second aliphatic conjugated diene monomers to obtain a second polymer preparation monomer mixture, adding 20% by weight of the second polymer preparation monomer mixture into a reaction kettle, introducing 20% by weight of the second aliphatic conjugated diene monomers, water and a second emulsifier into the reaction kettle, mixing and emulsifying, and preparing second polymer seed glue by emulsion copolymerization in the presence of 50% by weight of a second initiator; then adding the rest second polymer dropwise to prepare a monomer mixture, the rest second aliphatic conjugated diene monomer and an initiator, after 2 hours, continuing to keep the temperature and stir for reaction for 3 hours to prepare a second polymer emulsion finished product; the second emulsifier is sodium dodecyl benzene sulfonate; the second initiator is ammonium persulfate; the mass ratio of the second polymer preparation monomer mixture to the second emulsifier to the second initiator is 100:6:2; the reaction temperature of the emulsion copolymerization is 75 ℃, and the reaction time is 7h.
The preparation method of the lithium battery composite binder comprises the following steps: and mixing the first polymer emulsion and the second polymer emulsion according to a proportion, and uniformly stirring to obtain the lithium battery composite binder Si-Carxyl GD1332.
Example 4
A lithium battery composite binder comprises a mixture formed by mixing a first polymer emulsion and a second polymer emulsion in any proportion; the first polymer is a polymer formed by copolymerizing a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer capable of undergoing a free radical polymerization reaction with the monomers; the second polymer is a polymer formed by copolymerizing unsaturated carboxylic acid alkyl ester, second alkenyl aromatic monomer, acrylonitrile, vinyl beta-cyclodextrin quaternary ammonium salt, second aliphatic conjugated diene monomer and second other monomers capable of carrying out free radical polymerization reaction with the monomers;
the first other monomer is a mixture formed by mixing N-vinylcarbazole, 3- (1, 1-difluoroallyl) quinoxaline-2-alcohol and tetrahydrofurfuryl methacrylate according to a mass ratio of 1:1.8:1; the second other monomer is a mixture formed by mixing 2-acrylamide-2-methylpropanesulfonic acid, 4-propylene oxygen-2-hydroxybenzophenone and 2- (1-propylene-2-yl) benzo [ D ] oxazole according to a mass ratio of 1:1.8:3.
The mass ratio of the first aliphatic conjugated diene monomer to the first alkenyl aromatic monomer to the ethylenically unsaturated carboxylic acid monomer to the first other monomers in the preparation of the first polymer is 30:55:9:9; the first aliphatic conjugated diene monomer is a mixture formed by mixing 2-methyl-1, 3-butadiene, 1, 3-butadiene and 2, 3-dimethyl-1, 3-butadiene according to a mass ratio of 1:1:3; the first alkenyl aromatic monomer is a mixture formed by mixing vinyl benzene, vinyl toluene, styrene and alpha-methyl styrene according to a mass ratio of 1:2:1:3; the ethylenically unsaturated carboxylic acid monomer is a mixture formed by mixing acrylic acid, methacrylic acid and itaconic acid according to a mass ratio of 2:3:1.
The mass ratio of the unsaturated carboxylic acid alkyl ester, the second alkenyl aromatic monomer, the acrylonitrile, the vinyl beta-cyclodextrin quaternary ammonium salt, the second aliphatic conjugated diene monomer and the second other monomer of the second polymer is 25:23:4.5:3.5:4.5:11; the unsaturated carboxylic acid alkyl ester is a mixture formed by mixing ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate and dimethyl itaconate according to a mass ratio of 1:1:2:3; the second alkenyl aromatic monomer is a mixture formed by mixing 2-methyl-1, 3-butadiene, 1, 3-butadiene and 2, 3-dimethyl-1, 3-butadiene according to a mass ratio of 3:1:2; the second alkenyl aromatic monomer is a mixture formed by mixing styrene and alpha-methyl styrene according to a mass ratio of 3:5; the second aliphatic conjugated diene monomer is a mixture formed by mixing 2-methyl-1, 3-butadiene, 1, 3-butadiene and 2, 3-dimethyl-1, 3-butadiene according to a mass ratio of 1:2:1.
The preparation method of the first polymer emulsion comprises the following steps: uniformly mixing the first polymer preparation monomers to obtain a first polymer preparation monomer mixture, adding water and a first emulsifier, mixing and emulsifying, and preparing a first polymer emulsion finished product by emulsion copolymerization in the presence of a first initiator; the first emulsifier is a mixture formed by mixing sodium dodecyl sulfate, sodium dodecyl ether sulfate, ammonium dodecyl ether sulfate and sodium dodecyl benzene sulfonate according to a mass ratio of 1:1:3:2; the first initiator is a mixture formed by mixing potassium persulfate, sodium persulfate and ammonium persulfate according to a mass ratio of 3:1:2; the mass ratio of the first polymer preparation monomer mixture, the first emulsifier and the first initiator is 100:7:1.8; the reaction temperature of the emulsion copolymerization is 80 ℃ and the reaction time is 6h.
The preparation method of the second polymer emulsion comprises the following steps: uniformly mixing second polymer preparation monomers except for second aliphatic conjugated diene monomers to obtain a second polymer preparation monomer mixture, adding 20% by weight of the second polymer preparation monomer mixture into a reaction kettle, introducing 20% by weight of the second aliphatic conjugated diene monomers, water and a second emulsifier into the reaction kettle, mixing and emulsifying, and preparing second polymer seed glue by emulsion copolymerization in the presence of 50% by weight of a second initiator; then adding the rest second polymer dropwise to prepare a monomer mixture, the rest second aliphatic conjugated diene monomer and an initiator, after 2 hours, continuing to keep the temperature and stir for reaction for 3 hours to prepare a second polymer emulsion finished product; the second emulsifier is a mixture formed by mixing sodium dodecyl ether sulfate, ammonium dodecyl ether sulfate and sodium dodecyl benzene sulfonate according to a mass ratio of 1:3:5; the second initiator is a mixture formed by mixing potassium persulfate, sodium persulfate and ammonium persulfate according to a mass ratio of 1:2:1; the mass ratio of the second polymer preparation monomer mixture to the second emulsifier to the second initiator is 100:7:2.5; the reaction temperature of the emulsion copolymerization is 85 ℃ and the reaction time is 8.5h.
The preparation method of the lithium battery composite binder comprises the following steps: and mixing the first polymer emulsion and the second polymer emulsion according to a proportion, and uniformly stirring to obtain the lithium battery composite binder Si-Carxyl GD1333.
Example 5
A lithium battery composite binder comprises a mixture formed by mixing a first polymer emulsion and a second polymer emulsion in any proportion; the first polymer is a polymer formed by copolymerizing a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer capable of undergoing a free radical polymerization reaction with the monomers; the second polymer is a polymer formed by copolymerizing unsaturated carboxylic acid alkyl ester, second alkenyl aromatic monomer, acrylonitrile, vinyl beta-cyclodextrin quaternary ammonium salt, second aliphatic conjugated diene monomer and second other monomers capable of carrying out free radical polymerization reaction with the monomers;
the first other monomer is a mixture formed by mixing N-vinylcarbazole, 3- (1, 1-difluoroallyl) quinoxalin-2-ol and tetrahydrofurfuryl methacrylate according to a mass ratio of 1:2:1; the second other monomer is a mixture formed by mixing 2-acrylamide-2-methylpropanesulfonic acid, 4-propylene oxygen-2-hydroxybenzophenone and 2- (1-propylene-2-yl) benzo [ D ] oxazole according to a mass ratio of 1:2:3.
Preparation monomers of the first polymer comprise a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer in a mass ratio of 35:60:10:10; the first aliphatic conjugated diene monomer is 2-methyl-1, 3-butadiene; the first alkenyl aromatic monomer is vinyl benzene; the ethylenically unsaturated carboxylic acid monomer is acrylic acid.
The mass ratio of the unsaturated carboxylic acid alkyl ester, the second alkenyl aromatic monomer, the acrylonitrile, the vinyl beta-cyclodextrin quaternary ammonium salt, the second aliphatic conjugated diene monomer and the second other monomer of the second polymer is 30:25:5:4:5:12; the unsaturated carboxylic acid alkyl ester is ethyl methacrylate; the second alkenyl aromatic monomer is 2, 3-dimethyl-1, 3-butadiene; the second alkenyl aromatic monomer is alpha-methyl styrene; the second aliphatic conjugated diene monomer is 2-methyl-1, 3-butadiene.
The preparation method of the first polymer emulsion comprises the following steps: uniformly mixing first polymer preparation monomers except for first aliphatic conjugated diene monomers to obtain a first polymer preparation monomer mixture, adding 30% of the weight of the first polymer preparation monomer mixture into a reaction kettle, introducing 20% of first aliphatic conjugated diene monomers, water and a first emulsifier into the reaction kettle, mixing and emulsifying, preparing a first polymer seed adhesive by emulsion copolymerization in the presence of 50% of a first initiator by weight, simultaneously dropwise adding the rest of the first polymer preparation monomer mixture, the rest of the first aliphatic conjugated diene monomers and the rest of the initiator, and continuously preserving heat and stirring for reacting for 5 hours after 2 hours to obtain a first polymer emulsion finished product; the first emulsifier is dodecyl ether ammonium sulfate; the first initiator is sodium persulfate; the mass ratio of the first polymer preparation monomer mixture to the first emulsifier to the first initiator is 100:8:2; the reaction temperature of the emulsion copolymerization is 85 ℃ and the reaction time is 7h.
The preparation method of the second polymer emulsion comprises the following steps: uniformly mixing second polymer preparation monomers except for second aliphatic conjugated diene monomers to obtain a second polymer preparation monomer mixture, adding 20% by weight of the second polymer preparation monomer mixture into a reaction kettle, introducing 20% by weight of the second aliphatic conjugated diene monomers, water and a second emulsifier into the reaction kettle, mixing and emulsifying, and preparing second polymer seed glue by emulsion copolymerization in the presence of 50% by weight of a second initiator; then adding the rest second polymer dropwise to prepare a monomer mixture, the rest second aliphatic conjugated diene monomer and an initiator, after 2 hours, continuing to keep the temperature and stir for reaction for 3 hours to prepare a second polymer emulsion finished product; the second emulsifier is dodecyl ether ammonium sulfate; the second initiator is sodium persulfate; the mass ratio of the second polymer preparation monomer mixture to the second emulsifier to the second initiator is 100:8:3; the reaction temperature of the emulsion copolymerization is 90 ℃ and the reaction time is 9h.
The preparation method of the lithium battery composite binder comprises the following steps: and mixing the first polymer emulsion and the second polymer emulsion in proportion, and uniformly stirring to obtain the lithium battery composite adhesive.
Comparative example 1
A lithium battery composite binder has a formulation substantially the same as that of example 1, except that the first other monomer does not contain 3- (1, 1-difluoroallyl) quinoxalin-2-ol.
Comparative example 2
A lithium battery composite binder having a formulation substantially the same as in example 1 except that the second additional monomer does not comprise 2- (1-propen-2-yl) benzo [ D ] oxazole.
Meanwhile, in order to evaluate the specific technical effects of the lithium battery composite binder, performance tests are performed by using the lithium battery composite binder in the embodiment and the comparative example, and the test results are shown in table 1, and the test method is as follows: artificial graphite (six-purpose graphite, 12000 mesh, henan six-purpose graphite limited) is used as a negative electrode active material, and each group of binders is used to prepare the artificial graphite according to the mass ratio: thickener CMC (CMC 2200, macroxylonite, supplied by overseas electric international trade limited): carbon black conductive agent SP (switzerland SUPER high conductive carbon black upper P Li lithium battery conductive agent): binder=95.8:1.2:1.0:2.0 to prepare a negative electrode plate, and LiCoO is prepared according to the mass ratio 2 (supplied by Allatin, MDL: MFCD00049786, cat# L10451-2.5 kg): PVDF (Suwei PVDF Solef 5130, U.S.): carbon black conductive agent sp=95:2.5:2.5 to prepare positive pole pieceThe method comprises the steps of carrying out a first treatment on the surface of the According to the lithium ion battery assembled by the negative pole piece, the positive pole piece and the Celgard 2400-type diaphragm, constant-current charge and discharge tests are carried out, and the LiPF is used 6 Dissolving in a mixed solvent of EC/DEC/emc=2:3:1 at a concentration of 1 mol/l to form a nonaqueous electrolyte, wherein EC is ethylene carbonate, EMC is methylethyl carbonate, and DEC is diethyl carbonate; the charge termination voltage is 3.0-4.2V, the charge current is 850mAh, and the discharge current is 850mAh.
Peel strength test: the negative electrode sheet obtained in the previous step was cut into strips of 20mm×100mm, and a transparent adhesive tape (manufactured by 3M company) was attached to the electrode surface to fix the electrode sheet. The adhesive tape was peeled at a speed of 50 mm/min in the direction of 180℃according to JISK6854-2 test method for adhesive peel strength, and the average strength (mN/mm) was measured five times. The control group was a binder of styrene-butadiene rubber SBR (trade name: SN-307) commercially available from Sumitomo.
Electrolyte resistance was performed according to the following experimental method: 70g of each product is diluted to 20 weight percent of binder which is contained in solid, poured into a mould and transferred to an oven, and baked for 8 hours at 60 ℃, 4 hours at 90 ℃,2 hours at 120 ℃ and 15 minutes at 140 ℃ in sequence, thus obtaining the adhesive film. Then punching the adhesive film into a dumbbell shape, weighing the adhesive film by using a ten-thousandth balance, measuring the thickness of the adhesive film by using a micrometer, and recording related data as a first adhesive film for later use; and placing the first adhesive film into an aluminum plastic bag, injecting electrolyte with 40 times of the weight of the adhesive film, and sealing. And (5) transferring the packaged aluminum-plastic bag into a baking oven at 40 ℃ and baking for 15 days. Taking out the plastic-aluminum bag inner adhesive film, using water absorbing paper to absorb electrolyte on the surface of the adhesive film, weighing the electrolyte by using a ten-thousandth balance, measuring the thickness by using a micrometer, and recording related data as a second adhesive film for standby; the weight change rate and the thickness change rate are calculated respectively, and the electrolyte resistance is better as the weight change rate and the thickness change rate are smaller.
In order to further illustrate the electrochemical performance and the cycling stability of the product of each embodiment of the invention, the product of the embodiment 1 is taken as an example to carry out low-temperature EIS (alternating current impedance spectrum), normal-temperature and high-temperature (45 ℃) cycling test, and is compared with the product of the Rui-Wen 451B, the test reference standard UL1642 is adopted, the assembly method of the lithium ion battery is the same as that described above, the battery is charged and saturated according to the standard, then the battery is placed at-1 ℃ for 16 hours, and then the battery is discharged to 30% SOC at-1 ℃ under constant current of 0.2C, and the battery is placed for 2 hours; using an electrochemical workstation to test the battery by using a low-temperature alternating current impedance spectrum; the prepared batteries were charged and discharged at 25℃and 45℃for 650 weeks at 2℃using BK6016AR/2 secondary performance detection cabinets, respectively; rated capacity was observed under the same conditions. The test result shows that the impedance of the product of the embodiment 1 is 87.9mohm in the 30% SOC state, the impedance of the product of the Rui-Wen 451B is 110.5mohm in the 30% SOC state, and the temperature of the product of the embodiment 1 is minus 1 ℃; it can be seen that the product of example 1 of the present invention has a better impedance than the product of Rui Wen 451B at-1℃and 30% SOC. The rated capacity of the product of the embodiment 1 of the invention is 92% after 650 weeks of circulation at 25 ℃; the rated capacity of the product of the embodiment 1 of the invention is 90% after the product is cycled at 45 ℃ for 650 weeks; the rated capacity of the product of the Rui Wen 451B is 89% after 650 weeks of circulation at 25 ℃; the rated capacity of the product of the Rui Wen 451B is 89% after 650 weeks of circulation at 45 ℃; therefore, the product of the embodiment 1 of the invention has better cycle stability at normal temperature and high temperature (45 ℃).
As can be seen from table 1, the lithium battery composite binder disclosed in the examples of the present invention has better adhesion and electrolyte tolerance than the commercial products and comparative examples, and the lithium battery prepared by using the binder has more excellent electrochemical properties as a result of the synergistic effect of the various components. The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way; those of ordinary skill in the art will readily implement the invention as described above; however, those skilled in the art will appreciate that many modifications, adaptations, and variations of the present invention are possible in light of the above teachings without departing from the scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (7)
1. The lithium battery composite binder is characterized by comprising a mixture formed by mixing a first polymer emulsion and a second polymer emulsion in any proportion; the first polymer is a polymer formed by copolymerizing a first aliphatic conjugated diene monomer, a first alkenyl aromatic monomer, an ethylenically unsaturated carboxylic acid monomer and a first other monomer capable of undergoing a free radical polymerization reaction with the monomers; the second polymer is a polymer formed by copolymerizing unsaturated carboxylic acid alkyl ester, second alkenyl aromatic monomer, acrylonitrile, vinyl beta-cyclodextrin quaternary ammonium salt, second aliphatic conjugated diene monomer and second other monomers capable of carrying out free radical polymerization reaction with the monomers; the first other monomer is a mixture formed by mixing N-vinylcarbazole, 3- (1, 1-difluoroallyl) quinoxalin-2-alcohol and tetrahydrofurfuryl methacrylate according to the mass ratio of 1 (1-2): 1; the second other monomer is a mixture formed by mixing 2-acrylamide-2-methylpropanesulfonic acid, 4-propylene oxygen-2-hydroxy diphenyl ketone and 2- (1-propylene-2-yl) benzo [ D ] oxazole according to the mass ratio of 1 (1-2): 3;
the first aliphatic conjugated diene monomer is at least one of 2-methyl-1, 3-butadiene, 1, 3-butadiene and 2, 3-dimethyl-1, 3-butadiene; the first alkenyl aromatic monomer is at least one of vinyl toluene, styrene and alpha-methyl styrene; the ethylenically unsaturated carboxylic acid monomer is at least one of acrylic acid, methacrylic acid and itaconic acid; the unsaturated carboxylic acid alkyl ester is at least one of ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate and dimethyl itaconate; the second alkenyl aromatic monomer is at least one of styrene and alpha-methyl styrene; the second aliphatic conjugated diene monomer is at least one of 2-methyl-1, 3-butadiene, 1, 3-butadiene and 2, 3-dimethyl-1, 3-butadiene.
2. The lithium battery composite binder according to claim 1, wherein the mass ratio of the first polymer preparation monomer to the first aliphatic conjugated diene monomer, the first alkenyl aromatic monomer, the ethylenically unsaturated carboxylic acid monomer and the first other monomer is (15-35): (40-60): (3-10): (5-10).
3. The lithium battery composite binder according to claim 1, wherein the mass ratio of the unsaturated carboxylic acid alkyl ester, the second alkenyl aromatic monomer, the acrylonitrile, the vinyl beta-cyclodextrin quaternary ammonium salt, the second aliphatic conjugated diene monomer and the second other monomer of the second polymer is (10-30): (15-25): (3-5): (1-4): (3-5): (5-12).
4. The lithium battery composite binder according to claim 1, wherein the solid content of the first polymer emulsion is 15-65wt%, the glass transition temperature is-30-85 ℃, and the particle size is 50-1000nm; the solid content of the second polymer emulsion is 23-65wt%, the glass transition temperature is-35-88 ℃, and the granularity is 50-1000nm.
5. The lithium battery composite binder according to claim 1, wherein the preparation method of the first polymer emulsion comprises the following steps: uniformly mixing first polymer preparation monomers except for first aliphatic conjugated diene monomers to obtain a first polymer preparation monomer mixture, adding 20-30% of the weight of the first polymer preparation monomer mixture into a reaction kettle, introducing 20% of first aliphatic conjugated diene monomers, water and a first emulsifier into the reaction kettle, mixing and emulsifying, preparing a first polymer seed adhesive by emulsion copolymerization in the presence of 50% of a first initiator by weight, simultaneously dropwise adding the rest of the first polymer preparation monomer mixture, the rest of the first aliphatic conjugated diene monomers and the rest of the initiator, and continuously preserving heat and stirring for 3-5 hours after the completion of the dripping to prepare a first polymer emulsion finished product; the first emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl ether sulfate, ammonium dodecyl ether sulfate and sodium dodecyl benzene sulfonate; the first initiator is at least one of potassium persulfate, sodium persulfate and ammonium persulfate; the mass ratio of the first polymer preparation monomer mixture to the first emulsifier to the first initiator is 100 (2-8) (1-2); the reaction temperature of the emulsion copolymerization is 60-85 ℃ and the reaction time is 3-7h.
6. The lithium battery composite binder according to claim 1, wherein a second polymer preparation monomer mixture is obtained by uniformly mixing second polymer preparation monomers except for a second aliphatic conjugated diene monomer, 20% by weight of the second polymer preparation monomer mixture is added into a reaction kettle, 20% by weight of the second aliphatic conjugated diene monomer, water and a second emulsifier are introduced into the reaction kettle, and after mixing and emulsifying, a second polymer seed gel is prepared by emulsion copolymerization in the presence of 50% by weight of a second initiator; then adding the rest second polymer dropwise to prepare a monomer mixture, the rest second aliphatic conjugated diene monomer and an initiator, after 2 hours, continuing to keep the temperature and stir for reaction for 3 hours to prepare a second polymer emulsion finished product; the second emulsifier is one or more of sodium dodecyl ether sulfate, ammonium dodecyl ether sulfate and sodium dodecyl benzene sulfonate; the second initiator is at least one of potassium persulfate, sodium persulfate and ammonium persulfate; the mass ratio of the second polymer preparation monomer mixture to the second emulsifier to the second initiator is 100 (1-8) (1-3); the reaction temperature of the emulsion copolymerization is 50-90 ℃ and the reaction time is 5-9h.
7. A method for preparing the lithium battery composite binder according to any one of claims 1 to 6, comprising the steps of: and mixing the first polymer emulsion and the second polymer emulsion in proportion, and uniformly stirring to obtain the lithium battery composite adhesive.
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