CN117878327A - Positive electrode additive and positive electrode slurry of lithium ion battery and lithium ion battery - Google Patents
Positive electrode additive and positive electrode slurry of lithium ion battery and lithium ion battery Download PDFInfo
- Publication number
- CN117878327A CN117878327A CN202410041090.2A CN202410041090A CN117878327A CN 117878327 A CN117878327 A CN 117878327A CN 202410041090 A CN202410041090 A CN 202410041090A CN 117878327 A CN117878327 A CN 117878327A
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- Prior art keywords
- positive electrode
- additive
- lithium ion
- ion battery
- suspension
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- 239000000654 additive Substances 0.000 title claims abstract description 66
- 230000000996 additive effect Effects 0.000 title claims abstract description 66
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 35
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000725 suspension Substances 0.000 claims abstract description 32
- 239000002033 PVDF binder Substances 0.000 claims abstract description 27
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000003292 glue Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000005054 agglomeration Methods 0.000 claims abstract description 8
- 230000002776 aggregation Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 12
- 238000009736 wetting Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000006256 anode slurry Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 208000034693 Laceration Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- -1 lithium salt compound Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a positive electrode additive and positive electrode slurry of a lithium ion battery and the lithium ion battery, wherein the positive electrode additive is a suspension additive and is used for improving the overcharge prevention performance of the battery, and the positive electrode additive comprises a continuous phase and a disperse phase, wherein the disperse phase comprises lithium carbonate and/or lithium chloride crystal powder, the continuous phase is N-methylpyrrolidone NMP glue solution or NMP glue solution containing polyvinylidene fluoride (PVDF), the percentage of the disperse phase to the total mass of the suspension additive is 30-70%, the percentage of the polyvinylidene fluoride (PVDF) to the total mass of the suspension additive is 4-10%, and the solid content of the suspension additive is set to 30-80%. According to the invention, the powdery overcharge additive is firstly prepared into the uniformly dispersed suspension additive, and is fully wetted and dispersed and then added into the positive electrode slurry, so that the problems that large particles formed by agglomeration of the overcharge additive are easily scratched and scratched when the screen is blocked and coated due to the fact that the screen is deposited in the prior art are effectively solved, and the overcharge protection performance of the lithium ion battery is improved.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery positive electrode slurry, in particular to a lithium ion battery positive electrode additive, positive electrode slurry and a lithium ion battery.
Background
The high-rate cylindrical battery has higher safety performance due to the structural advantage, and is commonly used for power type product power supplies including electric tools. To improve the overcharge prevention performance of the battery, an overcharge additive is generally added to the positive electrode. Within a certain voltage range, the additive decomposes to generate gas, thereby increasing the battery polarization to reach a cut-off voltage in advance or opening a safety valve. The additive is usually an inorganic lithium salt compound, and is added into positive electrode slurry in a dry powder form, so that the additive is easy to agglomerate and difficult to achieve the effect of uniform dispersion, large particles formed by agglomeration cause poor content consistency of the additive in the battery core, scratches and lacerations are very easy to occur when the slurry is coated, particles are easy to deposit on a screen to cause screen blockage, and the input yield and the production efficiency are greatly reduced.
Disclosure of Invention
In order to solve the problem that the existing overcharge additive is added into positive electrode slurry in a dry powder form, and the overcharge additive is easy to agglomerate, the invention provides a positive electrode additive and positive electrode slurry of a lithium ion battery and the lithium ion battery.
In order to achieve the above object, the present invention provides a positive electrode additive for a lithium ion battery, which is characterized in that: the positive electrode additive is a suspension additive and used for improving the overcharge resistance of the battery, and comprises a continuous phase and a disperse phase, wherein the disperse phase comprises lithium carbonate and/or lithium chloride crystal powder, the continuous phase is N-methylpyrrolidone (NMP) glue solution or NMP glue solution containing polyvinylidene fluoride (PVDF), the percentage of the disperse phase in the total mass of the suspension additive is 30-70%, the percentage of the polyvinylidene fluoride (PVDF) in the total mass of the suspension additive is 4-10%, and the solid content of the suspension additive is set to 30-80%.
Preferably, the particle size of the lithium carbonate and/or lithium chloride crystal powder is 0.5 to 10 μm.
Preferably, the suspension additive is prepared by dispersing by adopting a planetary stirring device, the revolution speed of a stirrer is 25-40 rpm, the rotation speed is 2000-3000 rpm, and the stirring time is 1-2 h.
Preferably, an oily wetting dispersant which can be used in an NMP solvent system is added to the N-methylpyrrolidone (NMP) glue solution or the NMP glue solution containing polyvinylidene fluoride (PVDF).
Preferably, the oily wetting dispersant is one or a mixture of more of polyacrylonitrile, polystyrene and polyacrylic acid.
Preferably, the oily wetting dispersant accounts for 1-10% of the total mass of the suspension additive.
The invention also provides a lithium ion battery anode slurry, which is characterized in that: the suspension additive is added into the positive electrode slurry, and the suspension additive accounts for 0.7-3% of the total mass of the positive electrode slurry, can be uniformly dispersed in the positive electrode slurry, and does not generate agglomeration.
The invention also provides a lithium ion battery, which is characterized in that: the positive electrode plate is prepared by the positive electrode slurry, and the positive electrode additive disclosed in any one of claims 1 to 5 has good consistency in the lithium ion battery, so that the overcharge protection performance of the lithium ion battery is better.
The additive powder is directly added into the slurry to form agglomerated particles, and the main reasons are that the crystal powder particles are small, the surface free energy is large, and N-methyl pyrrolidone (NMP) glue solution or NMP glue solution containing polyvinylidene fluoride (PVDF) is difficult to sufficiently wet the powder, and mechanical force and shearing force generated in the stirring and dispersing process of the lithium battery positive electrode slurry are insufficient to break up the agglomerated particles into microparticles with the particle size of 0.5-10 mu m, the large particle size formed by agglomeration is 10-150 mu m, the screen is blocked by the screen caused by the deposition of the particles on the screen by adopting a screen with 100-150 meshes, and the particles enter a coating device by adopting a screen with lower mesh number to generate coating scratches and even scratch a current collector foil. Therefore, the additive powder is crushed and dispersed with NMP or NMP glue solution of PVDF in ultra-high solid content in advance, and the key point is high solid content. Such powder particles cannot be broken up if the dispersion is carried out with a lower solids content.
Compared with the prior art, the invention has the beneficial effects that: 1. the powdery additive is firstly prepared into a uniformly dispersed suspension additive, and is added into the positive electrode slurry after being fully wetted and dispersed, so that the slurry is not agglomerated into large particles again, the slurry fineness is more uniform, the problems that the large particles formed by agglomeration of the additive in the prior art are easy to scratch and scratch the current collector foil when the screen is blocked and coated due to the fact that the screen is deposited with the large particles are effectively solved, and the slurry processability is improved; 2. the prepared suspension additive is more uniformly dispersed in the positive electrode slurry, so that the overcharge protection performance of the lithium ion battery is improved, the consistency of the lithium ion batteries prepared by the same batch of positive electrode slurry can be effectively improved, and the yield of the lithium ion battery is improved.
Drawings
FIG. 1 is a graph showing the overcharge temperature test of three lithium ion cell samples prepared from the same batch of positive electrode slurry of example 1 of this invention;
FIG. 2 is a graph showing the overcharge temperature test of three lithium ion cell samples prepared from the same batch of positive electrode slurry of example 2 of this invention;
fig. 3 is a graph of overcharging temperature test for three lithium ion battery samples prepared from the same batch of positive electrode slurry of comparative example.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but is not intended to limit the scope of the present invention.
Examples
Positive electrode slurry raw material composition: the preparation method comprises the following steps of preparing raw materials by mass ratio of a positive electrode active material, a conductive agent, polyvinylidene fluoride, lithium carbonate crystal powder with particle size of 0.5-10 mu m and NMP solvent: 95%:2%:2%:1%:35%;
firstly, placing NMP solvent, 10% of total polyvinylidene fluoride and all lithium carbonate crystal powder into a first stirring cylinder, stirring for 1h at revolution speed of 35rpm and rotation speed of 2500rpm, and preparing a suspension additive with solid content of 40%; putting the positive electrode active material, the conductive agent and the rest polyvinylidene fluoride into a second stirring cylinder, and pre-mixing for 30min; and then placing the prepared suspension additive into a first stirring cylinder, adding a proper amount of NMP solvent to adjust the slurry to a proper kneading state, stirring at a revolution speed of 35rpm and a rotation speed of 500rpm for 100-120 min, scraping, finally adding the rest NMP solvent, continuously stirring at the revolution speed of 25rpm and the rotation speed of 1800rpm for 1.5h, vacuumizing to-0.09 MPa, stirring at the revolution speed of 25rpm and the rotation speed of 2500rpm for 2h, adjusting the viscosity to 4000-700 mpa.s, sieving with a 150-mesh screen, and discharging to prepare the required anode slurry.
And uniformly coating the prepared positive electrode slurry on an aluminum foil to prepare a positive electrode plate, and preparing the lithium ion battery by matching the positive electrode plate with a negative electrode plate.
Examples
Positive electrode slurry raw material composition: the preparation method comprises the following steps of preparing raw materials by mass ratio of positive electrode active material, conductive agent, polyvinylidene fluoride, lithium chloride crystal powder with particle size of 0.5-10 mu m, polyacrylonitrile and NMP solvent: 98%:3%:3%:2%:0.2%:50%;
firstly, 10% of NMP solvent, 10% of total polyvinylidene fluoride, all lithium chloride crystal powder and all polyacrylonitrile are put into a second stirring tank, stirring is carried out for 2 hours at a revolution speed of 35rpm and a rotation speed of 2500rpm, a suspension additive with a solid content of 70% is prepared, the anode active material, the conductive agent and the rest polyvinylidene fluoride are put into a first stirring tank, firstly, dry premixing is carried out for 30 minutes, then the prepared suspension additive is put into the first stirring tank, a proper amount of NMP solvent is added to adjust the slurry to a proper kneading state, stirring is carried out for 100-120 minutes at a revolution speed of 30rpm, scraping is carried out, stirring is carried out for 2 hours at a revolution speed of 25rpm, vacuumizing is carried out to-0.09 MPa, stirring is carried out for 2.5 hours at a revolution speed of 25rpm, the viscosity is regulated to 4000-700 mpa.s, and then, sieving and discharging is carried out through a 150-mesh sieve, so that the required anode slurry is prepared.
And uniformly coating the prepared positive electrode slurry on an aluminum foil to prepare a positive electrode plate, and preparing the lithium ion battery by matching the positive electrode plate with a negative electrode plate.
Comparative example:
positive electrode slurry raw material composition: the preparation method comprises the following steps of preparing raw materials by mass ratio of a positive electrode active material, a conductive agent, polyvinylidene fluoride, lithium carbonate crystal powder with particle size of 0.5-10 mu m and NMP solvent: 95%:2%:2%:1%:35%;
adding an anode active material, a conductive agent, polyvinylidene fluoride and lithium carbonate crystal powder into a stirring tank, carrying out dry premixing for 30min, adding a proper amount of NMP solvent to adjust the slurry to a proper kneading state, stirring for 100-120 min at a revolution speed of 35rpm and a rotation speed of 500rpm, and scraping; adding NMP solvent to slurry design solid content, stirring for 1-2 h at revolution speed of 25rpm and rotation speed of 1800rpm, vacuumizing to-0.09 MPa, stirring for 2-2.5 h at revolution speed of 25rpm and rotation speed of 2500rpm, regulating viscosity to 4000-7000mpa.s, sieving with 150 mesh screen, and discharging to obtain the required anode slurry.
And uniformly coating the prepared positive electrode slurry on an aluminum foil to prepare a positive electrode plate, and preparing the lithium ion battery by matching the positive electrode plate with a negative electrode plate.
And (3) performance detection:
(1) The positive electrode slurry coating effect on the positive electrode sheets prepared in example 1, example 2 and comparative example was measured, and the measured effect is shown in Table 1
TABLE 1
As can be seen from Table 1, the surface quality of the positive electrode sheet coated with the positive electrode slurry using the suspension additive of the present invention was greatly improved relative to the comparative example.
(2) Three samples of the lithium ion batteries prepared in example 1, example 2 and comparative example were subjected to overcharge temperature test, and the test results are shown in table 2 and fig. 1, 2 and 3.
TABLE 2
As can be seen from table 2 and fig. 1, 2 and 3, the lithium ion batteries prepared in example 1 and example 2 of the present invention have significantly improved overcharge temperature uniformity relative to the lithium ion batteries prepared in comparative examples.
Therefore, the invention can effectively solve the problems that large particles formed by agglomeration of the overcharge additive are deposited on a screen to cause the screen to be blocked and the current collector foil to be easily scratched and scratched when the screen is coated by the agglomeration of the powder overcharge additive, and improves the processing performance of the slurry by firstly preparing the powder overcharge additive into the uniformly dispersed suspension additive, fully wetting and dispersing the suspension additive and then adding the suspension additive into the positive slurry; the prepared suspension additive is more uniformly dispersed in the positive electrode slurry, so that the overcharge protection performance of the lithium ion battery is improved, the consistency of the lithium ion batteries prepared by the same batch of positive electrode slurry can be effectively improved, and the yield of the lithium ion battery is improved.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and substitutions can be made by those skilled in the art without departing from the technical principles of the present invention, and these modifications and substitutions should also be considered as being within the scope of the present invention.
Claims (8)
1. A positive electrode additive of a lithium ion battery is characterized in that: the positive electrode additive is a suspension additive and used for improving the overcharge resistance of the battery, and comprises a continuous phase and a disperse phase, wherein the disperse phase comprises lithium carbonate and/or lithium chloride crystal powder, the continuous phase is N-methylpyrrolidone (NMP) glue solution or NMP glue solution containing polyvinylidene fluoride (PVDF), the percentage of the disperse phase in the total mass of the suspension additive is 30-70%, the percentage of the polyvinylidene fluoride (PVDF) in the total mass of the suspension additive is 4-10%, and the solid content of the suspension additive is set to 30-80%.
2. The positive electrode additive for lithium ion batteries according to claim 1, wherein: the particle size of the lithium carbonate and/or lithium chloride crystal powder is 0.5-10 mu m.
3. The positive electrode additive for lithium ion batteries according to claim 1, wherein: the suspension additive is prepared by adopting planetary stirring equipment in a dispersing way, the revolution speed of a stirrer is 25-40 rpm, the rotation speed is 2000-3000 rpm, and the stirring time is 1-2 h.
4. The positive electrode additive for lithium ion batteries according to claim 1, wherein: the N-methyl pyrrolidone (NMP) glue solution or the NMP glue solution containing polyvinylidene fluoride (PVDF) is added with oily wetting dispersant which can be used for NMP solvent system.
5. The positive electrode additive for lithium ion batteries according to claim 4, wherein: the oily wetting dispersant is one or a mixture of more of polyacrylonitrile, polystyrene and polyacrylic acid.
6. The positive electrode additive for lithium ion batteries according to claim 5, wherein: the oily wetting dispersant accounts for 1-10% of the total mass of the suspension additive.
7. The positive electrode slurry of the lithium ion battery is characterized in that: the suspension additive as claimed in any one of claims 1 to 6 is added into the positive electrode slurry, and the suspension additive accounts for 0.7 to 3 percent of the total mass of the positive electrode slurry, can be uniformly dispersed in the positive electrode slurry, and does not generate agglomeration.
8. A lithium ion battery, characterized in that: the positive electrode plate is prepared by the positive electrode slurry according to claim 4, and the positive electrode additive according to any one of claims 1 to 5 has good consistency in the lithium ion battery, so that the overcharge protection performance of the lithium ion battery is better.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410041090.2A CN117878327A (en) | 2024-01-11 | 2024-01-11 | Positive electrode additive and positive electrode slurry of lithium ion battery and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410041090.2A CN117878327A (en) | 2024-01-11 | 2024-01-11 | Positive electrode additive and positive electrode slurry of lithium ion battery and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117878327A true CN117878327A (en) | 2024-04-12 |
Family
ID=90582576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410041090.2A Pending CN117878327A (en) | 2024-01-11 | 2024-01-11 | Positive electrode additive and positive electrode slurry of lithium ion battery and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117878327A (en) |
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2024
- 2024-01-11 CN CN202410041090.2A patent/CN117878327A/en active Pending
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