CN115975171B - Polyether ester plasticizer and application thereof in field of lithium battery preparation - Google Patents
Polyether ester plasticizer and application thereof in field of lithium battery preparation Download PDFInfo
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- CN115975171B CN115975171B CN202211628813.6A CN202211628813A CN115975171B CN 115975171 B CN115975171 B CN 115975171B CN 202211628813 A CN202211628813 A CN 202211628813A CN 115975171 B CN115975171 B CN 115975171B
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Abstract
The invention claims a polyether ester plasticizer and application thereof in the field of lithium battery preparation, and the structural formula is as follows: r is R 1 O(C 2 H 4 O) m (C 3 H 6 O) n ‑C(O)‑R 2 . The polyether ester structure of the invention contains ester groups, and the addition of the plasticizer containing ester groups increases the distance between polymer molecular chains such as binder and the like in the battery slurry, weakens the interaction force between the polymer molecular chains to different degrees, i.e. reduces the Van der Waals force between the binder molecular chains, thereby increasing the flexibility of the positive electrode plate and preventing the cracking caused by the excessive stress of the binder molecules in the drying process.
Description
Technical Field
The invention relates to a polyether ester plasticizer, in particular to a plasticizer applied to positive electrode slurry of a lithium battery, and belongs to the technical field of lithium ion batteries.
Background
The lithium ion battery has the advantages of large specific energy, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like, and has wide application in the fields of aviation, national defense, automobiles, 3C and the like.
The lithium ion battery consists of a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the prepared slurry is required to be coated on an aluminum foil to prepare the positive electrode and the negative electrode respectively during forming, so that the composition and the characteristics of the slurry are directly related to the coating quality, and in view of the current higher and higher requirements on the capacity of the lithium ion battery, the common solution is to increase the proportion of electrode active substances in the slurry or thick coating of the slurry, but the problem that the proportion of the electrode active substances in the slurry can relate to the fluidity of the slurry is solved, and the slurry is easy to leak white or crack during winding and folding after thick coating, so that the flexibility of a pole piece is required to be increased.
At present, the method for increasing the toughness of the slurry and further achieving the purpose of softening by adding plasticizers such as dimethyl phthalate, dioctyl phthalate and the like is available in the industry, but the addition amount of the plasticizers is high, volatilization is not thorough, and the residual plasticizers easily influence the performance of the electrolyte. The organosilicon plasticizer increases unused elements in the battery slurry due to the silicon element, and the safety of the organosilicon plasticizer is hidden to be further evaluated.
Disclosure of Invention
Aiming at the problems that the anode slurry of the lithium ion battery is insufficient in toughness and flexibility during thick coating and the electrode plate is easy to leak white or crack during winding and folding, the invention provides a polyether ester plasticizer and application thereof in the field of lithium battery preparation
The technical scheme for solving the technical problems is as follows:
a polyetherester plasticizer having the structural formula:
R 1 O(C 2 H 4 O) m (C 3 H 6 O) n -C(O)-R 2
wherein R is 1 Represents any one of the following groups:
phenyl group,
R 2 Represents a C8-C18 alkyl group;
m represents an integer of 5 to 20; n represents an integer of 0 to 10.
Preferably, R 1 Representation of
Any one of the following.
Preferably, R 2 Represents a C8-C12 alkyl group.
Preferably, m represents an integer of 10 to 15.
Alkyl, C as described in the present invention 5 H 11 、C 7 H 15 、C 8 H 17 、C 10 H 21 The radicals may be linear or branched, and may be, for example, C 5 H 11 Pentyl, such as n-pentyl, isopentyl or neopentyl; c8 alkyl-octyl radicals, such as the n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2-dimethylhexyl, 3-dimethylhexyl, 2, 4-dimethylhexyl, 2, 5-dimethylhexyl, 3, 4-dimethylhexyl radicalMethyl hexyl, 3-ethyl hexane, 2, 3-trimethyl pentyl, 2, 4-trimethyl pentyl, and the like.
The polyether ester plasticizer of the invention can be obtained by the following preparation method:
(1) R is added from a charging port of the reaction kettle 1 OH and potassium hydroxide, testing pressure, after air leakage is confirmed, replacing with nitrogen for three times, pumping the pressure to the lowest, and closing the vacuum valve;
(2) Adding calculated amounts of ethylene oxide and propylene oxide into a reaction kettle, slowly heating to 80-130 ℃, opening stirring, reducing the reaction pressure to 0 after the reaction is finished, and carrying out neutralization refining after reducing the temperature to obtain polyether;
(3) Refined polyether and R 2 Adding COOH and concentrated sulfuric acid catalyst into a reaction kettle, heating to 130-180 ℃ while stirring, and carrying out esterification reaction to obtain the target product polyether ester.
The polyether ester plasticizer provided by the invention has the beneficial effects that:
(1) The polyether ester structure contains ester groups, and the addition of the plasticizer containing the ester groups increases the distance between polymer molecular chains such as the binder in the battery slurry, weakens the interaction force between the polymer molecular chains to different degrees, namely reduces the Van der Waals force between the binder molecular chains, thereby increasing the flexibility of the positive electrode plate and preventing the cracking caused by overlarge stress of the binder molecules in the drying process;
(2) By adjusting R in the polyether ester structure 1 、R 2 The molecular chain has certain elasticity and further has a lubricating function, so that the problem of cracking and light leakage when the pole piece is wound and folded is effectively solved;
(3) The end part of the polyether ester contains a benzene ring structure, so that the conductive agent is uniformly dispersed, the conductive agent is uniformly distributed while the flexibility is enhanced, the lubricating effect is further achieved, and the performance of a battery cell is not influenced.
The invention also discloses a lithium ion battery anode slurry, which comprises the polyether ester plasticizer.
Preferably, the positive electrode slurry further contains a positive electrode active material and a conductive agent.
Preferably, the positive electrode active material is one or more of lithium cobaltate, lithium nickel cobalt manganate, lithium iron manganese phosphate and lithium iron phosphate; the conductive agent is one or more selected from conductive carbon black, superconductive carbon black, conductive graphite, acetylene black, ketjen black, graphene and carbon nano tube.
Preferably, the positive electrode slurry further comprises a binder and an organic solvent, wherein the binder is one or two of vinylidene fluoride homopolymer and vinylidene fluoride copolymer, and the organic solvent is N-methylpyrrolidone.
The invention also discloses a positive pole piece of the lithium ion battery, and the surface of the positive pole piece is coated with the positive pole slurry of the lithium ion battery.
The invention also discloses a lithium ion battery, which comprises the positive electrode plate.
Detailed Description
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and not to limit the scope of the invention.
Table 1 structural formula of polyetherester plasticizer used in examples
Example 1: effect in wet pulping process
The specific preparation steps of the lithium battery positive electrode slurries of the experimental groups 1-5 and the control group 1 are as follows:
1) Mixing and stirring the binder and the organic solvent uniformly to obtain a glue solution A;
2) Adding the plasticizers A-E in the table 1 into the glue solution A respectively and stirring uniformly to obtain a glue solution B;
3) Adding a conductive agent into the glue solution B to obtain conductive agent slurry;
4) And adding the positive electrode active material into the conductive agent slurry to obtain positive electrode slurry.
The weight ratio of the raw materials in the method is as follows: conductive agent: and (3) a plasticizer: binder=96:2.3:0.3:1.4; the positive electrode active material is nickel cobalt lithium manganate of New Material technology Co., ltd. Of Analli of Tianjin, the conductive agent is formed by mixing conductive carbon black and carbon nano tube according to a mass ratio of 1:1, the binder is polyvinylidene fluoride, the organic solvent is N-methyl pyrrolidone, and the plasticizers used in the experimental groups 1-5 are respectively plasticizer A, plasticizer B, plasticizer C, plasticizer D and plasticizer E.
The plasticizer in control group 1 was dioctyl phthalate, and the other components of the slurry were the same as those in experimental groups 1-5.
The preparation process of the positive electrode plate comprises the following steps:
coating at a coating speed of 40m/min by a knife coater, uniformly coating electrode slurry on the front and back surfaces of an aluminum foil with a thickness of 12 mu m, baking and drying at 105 ℃, and removing the solvent to obtain the electrode plate in the embodiment of the invention.
The test procedure was as follows:
1. folding and testing the positive pole piece: and after the positive pole piece is folded in half, rolling the positive pole piece back and forth for 3 times by using a compression roller with the weight of 2kg, then paving the positive pole piece flat, repeating the operation until light leakage occurs at the folded part, and recording the folding times. Each group was tested 5 times and averaged.
2. Resistance test of positive pole piece: the resistance of the positive electrode sheet was tested 5 times per group using a CRM-01 sheet resistance tester, and an average was taken.
Table 2 electrode sheet test effects of experimental groups 1-5 and control group 1
| Test object | Slurry solid content% | Positive electrode slurry coating process | Folding light leakage times | Resistor (omega) |
| Experiment group 1 | 68 | Good quality | 4 times | 0.7 |
| Experiment group 2 | 70 | Good quality | 4 times | 0.8 |
| Experiment group 3 | 72 | Good quality | 3 times | 0.6 |
| Experiment group 4 | 71 | Good quality | 4 times | 0.9 |
| Experiment group 5 | 73 | Good quality | 5 times | 0.7 |
| Control group 1 | 69 | Difference of difference | 2 times | 0.8 |
As can be seen from the data in Table 1, after the plasticizer of the present invention is added in the experimental groups 1 to 5, compared with the control group 1, the effect of the slurry coating process is obviously improved, and the number of times of double-folded light leakage is obviously improved, which indicates that the plasticizer of the present invention has obvious effect of increasing flexibility and toughness for the positive electrode sheet obtained by the wet pulping process.
Example 2: effect in dry pulping process
The specific preparation process of the lithium battery positive electrode slurries of the experimental groups 6-10 and the control group 2 is as follows:
1) Dry-mixing the binder, the conductive agent and the positive electrode active material to obtain uniformly mixed powder;
2) Adding part of organic solvent into the powder, and uniformly stirring to obtain initial slurry A;
3) Adding the plasticizer in the invention into the initial slurry A, and uniformly stirring;
4) And on the basis of the step 3), adding the rest organic solvent, and uniformly stirring to obtain the positive electrode slurry.
Wherein, the weight ratio of each raw material is that the positive electrode active material: conductive agent: and (3) a plasticizer: binder = 97:1.5:0.3:1.2; the positive electrode active material is lithium iron phosphate, the conductive agent is formed by mixing conductive carbon black and carbon nano tubes according to the mass ratio of 1:1, the binder is polyvinylidene fluoride, the organic solvent is N-methyl pyrrolidone, and the plasticizers used in examples 6-10 are respectively plasticizer A, plasticizer B, plasticizer C, plasticizer D and plasticizer E.
The plasticizer in control group 2 was dioctyl phthalate, and the other components of the slurry were the same as those in experimental groups 6-10.
The preparation process of the positive electrode plate comprises the following steps:
coating at a coating speed of 40m/min by a knife coater, uniformly coating electrode slurry on the front and back surfaces of an aluminum foil with a thickness of 12 mu m, baking and drying at 105 ℃, and removing the solvent to obtain the electrode plate in the embodiment of the invention.
The test procedure was as follows:
1. folding and testing the positive pole piece: and after the positive pole piece is folded in half, rolling the positive pole piece back and forth for 3 times by using a compression roller with the weight of 2kg, then paving the positive pole piece flat, repeating the operation until light leakage occurs at the folded part, and recording the folding times. Each group was tested 5 times and averaged.
2. Resistance test of positive electrode membrane: and testing the resistance of the positive electrode diaphragm by using a CRM-01 pole piece resistance tester. Each group was tested 5 times and averaged.
TABLE 3 electrode sheet test effects for experimental groups 6-10 and control group 2
| Test object | Slurry solid content% | Positive electrode slurry coating process | Folding light leakage times | Resistor (omega) |
| Experiment group 1 | 60 | Good quality | 5 times | 0.8 |
| Experiment group 2 | 63 | Good quality | 4 times | 0.7 |
| Experiment group 3 | 65 | Good quality | 3 times | 0.6 |
| Experiment group 4 | 67 | Good quality | 4 times | 0.8 |
| Experiment group 5 | 68 | Good quality | 4 times | 0.7 |
| Control group 1 | 64 | Difference of difference | 1 time | 0.9 |
As can be seen from the data in Table 3, after the plasticizer of the present invention is added to the positive electrode slurry of the experimental group 6-10, compared with the control group 2, the effect of the slurry coating process is significantly improved, and the number of times of folded light leakage is significantly increased, which indicates that the plasticizer of the present invention also has significantly increased flexibility and toughness for the positive electrode sheet obtained by the dry pulping process.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A polyetherester plasticizer characterized by the following structural formula:
R 1 O(C 2 H 4 O) m (C 3 H 6 O) n -C(O)-R 2
wherein R is 1 Represents any one of the following groups:
phenyl group,
R 2 Represents a C8-C18 alkyl group;
m represents an integer of 5 to 20; n represents an integer of 0 to 10.
2. The polyetherester plasticizer of claim 1, wherein R 1 Representation of
Any one of the following.
3. The polyetherester plasticizer according to claim 1 or 2, wherein R 2 Represents a C8-C12 alkyl group.
4. A polyetherester plasticizer according to claim 1 or 2 wherein m represents an integer from 10 to 15.
5. A polyetherester plasticizer according to claim 3 wherein m represents an integer from 10 to 15.
6. A lithium ion battery positive electrode slurry comprising the polyetherester plasticizer of any one of claims 1 to 5.
7. The positive electrode slurry for a lithium ion battery according to claim 6, further comprising a positive electrode active material and a conductive agent.
8. The positive electrode slurry for a lithium ion battery according to claim 7, wherein the positive electrode active material is one or more of lithium cobaltate, lithium nickel cobalt manganate, lithium iron manganese phosphate and lithium iron phosphate; the conductive agent is one or more selected from conductive carbon black, superconductive carbon black, conductive graphite, acetylene black, ketjen black, graphene and carbon nano tube.
9. The positive electrode slurry of a lithium ion battery according to any one of claims 6 to 8, further comprising a binder and an organic solvent, wherein the binder is one or both of vinylidene fluoride homopolymer and vinylidene fluoride copolymer, and the organic solvent is N-methylpyrrolidone.
10. A positive electrode sheet of a lithium ion battery, characterized in that the surface of the positive electrode sheet is coated with the positive electrode slurry of a lithium ion battery according to any one of claims 6 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2394817C1 (en) * | 2008-12-29 | 2010-07-20 | Общество с ограниченной ответственностью "Промышленно-торговая компания ТАНТАНА" г. Стерлитамак | Method of producing corrosion inhibitors |
| CN102977331A (en) * | 2012-11-15 | 2013-03-20 | 山东德仕化工集团有限公司 | Preparation method for efficient oil-soluble macromolecular demulsifier |
| CN113214466A (en) * | 2021-06-04 | 2021-08-06 | 浙江皇马科技股份有限公司 | Tristyryl phenol block polyether, sulfate ammonium salt and preparation method thereof |
| CN115141376A (en) * | 2022-08-01 | 2022-10-04 | 深圳市皓飞实业有限公司 | Dispersing agent for lithium ion battery anode slurry and application thereof |
| CN115340671A (en) * | 2021-05-12 | 2022-11-15 | 联泓(江苏)新材料研究院有限公司 | Low-pour-point block polyether and preparation method and application thereof |
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- 2022-12-18 CN CN202211628813.6A patent/CN115975171B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2394817C1 (en) * | 2008-12-29 | 2010-07-20 | Общество с ограниченной ответственностью "Промышленно-торговая компания ТАНТАНА" г. Стерлитамак | Method of producing corrosion inhibitors |
| CN102977331A (en) * | 2012-11-15 | 2013-03-20 | 山东德仕化工集团有限公司 | Preparation method for efficient oil-soluble macromolecular demulsifier |
| CN115340671A (en) * | 2021-05-12 | 2022-11-15 | 联泓(江苏)新材料研究院有限公司 | Low-pour-point block polyether and preparation method and application thereof |
| CN113214466A (en) * | 2021-06-04 | 2021-08-06 | 浙江皇马科技股份有限公司 | Tristyryl phenol block polyether, sulfate ammonium salt and preparation method thereof |
| CN115141376A (en) * | 2022-08-01 | 2022-10-04 | 深圳市皓飞实业有限公司 | Dispersing agent for lithium ion battery anode slurry and application thereof |
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